Citation
Metallo-porphyrin containing zirconium phosphonate thin films

Material Information

Title:
Metallo-porphyrin containing zirconium phosphonate thin films structure and catalysis
Creator:
Lee, Christine Marie Nixon, 1973-
Publication Date:
Language:
English
Physical Description:
xiv, 171 leaves : ill. ; 29 cm.

Subjects

Subjects / Keywords:
Catalysis ( jstor )
Chlorides ( jstor )
Chromophores ( jstor )
Imidazoles ( jstor )
Ligands ( jstor )
Molecules ( jstor )
Phosphonic acids ( jstor )
Porphyrins ( jstor )
Solvents ( jstor )
Zirconium ( jstor )
Chemistry thesis, Ph. D ( lcsh )
Dissertations, Academic -- Chemistry -- UF ( lcsh )
Genre:
bibliography ( marcgt )
theses ( marcgt )
non-fiction ( marcgt )

Notes

Thesis:
Thesis (Ph. D.)--University of Florida, 2000.
Bibliography:
Includes bibliographical references (leaves 164-170).
General Note:
Printout.
General Note:
Vita.
Statement of Responsibility:
by Christine Marie Nixon Lee.

Record Information

Source Institution:
University of Florida
Holding Location:
University of Florida
Rights Management:
Copyright [name of dissertation author]. Permission granted to the University of Florida to digitize, archive and distribute this item for non-profit research and educational purposes. Any reuse of this item in excess of fair use or other copyright exemptions requires permission of the copyright holder.
Resource Identifier:
024895731 ( ALEPH )
45427191 ( OCLC )

Downloads

This item has the following downloads:


Full Text











METALLO-PORPHYRIN CONTAINING ZIRCONIUM PHOSPHONATE
THIN FILMS: STRUCTURE AND CATALYSIS













By

CHRISTINE MARIE NIXON LEE


A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY

UNIVERSITY OF FLORIDA


2000














ACKNOWLEDGMENTS


First, I would like to thank some of the teachers who have pointed me toward

chemistry and supported me in this long educational adventure. I thank Mr. Roger

Craig from Lexington High School, for being so excited about chemistry, and Dr. Jim

McCargar, for being a tireless ambassador of general and physical chemistry, and for

encouraging (pushing?) me to pursue research opportunities outside of Baldwin-

Wallace College. I would also like to thank Dr. Gary Kosloski, who cared about my

music even after I defected to the other half of the liberal arts and sciences. And to

Dr. John West and Dr. William Samuels, I extend many thanks for accepting me into

their research programs and giving me two unique and valuable perspectives on

research outside of the academic environment.

I must thank Dr. Dan Talham for his patience, the limits of which, I have

surely tested. I would also like to thank him for accepting a physical polymer

chemistry convert and for teaching me to appreciate materials and surface chemistry.

I would also like to thank him for his time and effort in encouraging all of us to be

organized and effective speakers and writers. For that, I will be eternally grateful.

I could not have completed this document or the research that it describes

without the collaborative assistance from the Bujoli group in Nantes, France.

Especially to Fabrice Odobel, who has contributed significant time and energy to








making and teaching others to make the porphyrins and ligands on which this

dissertation is focused, Merci!

Quick notes of thanks are also due to the Butler Polymer Research

Laboratories for sharing their instrumentation and to Eric Lambers and the Major

Analytical Instrumentation Center for allowing me to use the XPS. Also, thanks to

Joe and Raymond in the chemistry department machine shop for working with me on

designing and building the catalysis flow cells.

Without many wonderful friends, my time at University of Florida would have

been much less enjoyable. So, I thank Louann Troutman, Tracey Hawkins, Dean and

Annie Welsh, Denise Main, and Debby Tindall, and of course, Jen Batten and Leroy

Kloeppner (and Alex) the greatest of friends. I owe Jen and Leroy special thanks,

not only for their efforts in editing this dissertation, but also for their support and love

along the way.

And lastly, my family. All the gratitude in the world goes to my mom and dad,

Pat and Ron, and to my brothers Joe and John and my soon-to-be sister, Jullia. And to

my grandmothers, Evelyn Nixon and Margaret Loeber, and in memory of my

Grandpas Bill and Lee. I have been truly blessed. Thanks, too, to my new family,

George and Agnes, Brian and Greg Lee who are the best second family I could

imagine.

To my husband, Larry, my best friend and biggest fan, I owe more thanks than

can be expressed.















TABLE OF CONTENTS

page

ACKN OW LEDGM EN TS ................................................................................................. ii

LIST O F TA BLES ....................................................................................... ............... vii

LIST O F FIG U RES ................................................................................................... viii

A BSTRA CT.......................................................................................... ........................... iii

CHAPTERS

1 INTRODUCTION .................................... ...................................... 1

1.1 U ltrathin Film s........................................................................................ 1
1.1.1 Langmuir-Blodgett Films and Characterization ..........................3
1.1.2 Self-assembled Films ................................................................15
1.2 Hybrid Organic/Inorganic Ultrathin Films Based on Layered Solids .......16
1.2.1 Background.................................................... ... ......... 16
1.2.2 Self-assembled Films Incorporating Metal Phosphonate
B inding..................................................... ................... 19
1.2.3 Metal Phosphonate Langmuir-Blodgett Films............. ........20
1.2.4 Dual-Function Langmuir-Blodgett Films ......................................23
1.3 Background on Porphyrins ...................................................................24
1.3.1 Optical Behavior of Porphyrins ................................. ...............24
1.3.2 Background on Manganese Porphyrins ...................................33
1.3.3 Immobilization of Porphyrins .....................................................35
1.3.4 Heterocyclic Ligand Cocatalysts ........................................ ...36
1.4 Dissertation Overview ............................................................... .......... 38

2 EXPERIMENTAL ...............................................................................................42

2.1 Langmuir-Blodgett and Self-Assembled Film Preparation Procedure......42
2.1.1 General Langmuir-Blodgett and Self-Assembly Procedures.........42
2.1.1 Characterization ................................................................. 46
2.2 Porphyrin Films .................................................................................48
2.2.1 Palladium Porphyrin Films...................................... ............48
2.2.2 Manganese Porphyrin Films ........................................................49









2.2.3 Manganese Porphyrin/Imidazole Mixed Films..............................51
2.3 C atalysis..................................................................................................... 53
2.3.1 Catalysis using PhIO as an oxidant........................................53
2.3.2 Catalysis using Peroxides as oxidants....................................57


3 PALLADIUM PORPHYRIN CONTAINING ZIRCONIUM PHOSPHONATE
THIN FILM S.. ................................................................................................ 58

3.1 Background on Palladium Porphyrin Films...............................................58
3.2 R esults............................................................................ ........................61
3.2.1 UV-vis of Palladium Porphyrin Solutions...................................61
3.2.2 Langmuir Monolayers of Palldium Porphyrins ...........................63
3.2.3 Langmuir-Blodgett Films .........................................................69
2.3.3 Conclusions.................................................................... ..............79


4 MANGANESE PORPHYRIN CONTAINING ZIRCONIUM
PHOSPHONATE THIN FILMS ...................................................................... 83

4.1 Background ........................................................ ............. ...................... 83
4.2 UV-vis Behavior of MnTPPs...................................................................85
4.2.1 Solution studies.............................................. ..................85
4.2.2 Langmuir Monolayers..................................................................93
4.2.3 Langmuir-Blodgett Films of pure MnP4 ......................................95
4.2.4 Self-assembled films of MnP4...................................................100
4.3 C onclusions..............................................................................................106


5 INCORPORATION OF AN IMIDAZOLE LIGAND INTO MANGANESE
PORPHYRIN CONTAINING ZIRCONIUM PHOSPHONATE
TH IN FILM S.................................................................................................... 109

5.1 Background.... ...... .. ........ ....................................................................... 109
5.2 Solution Studies .................................................................................. 113
5.2.1 MnPO and MnP4 with ImH.......................................... ......... 113
5.2.2 MnP4 and MnPO with ImODPA................................................ 115
5.3 Film Studies .......................................................... .............................. 117
5.3.1 Langmuir-Blodgett Films containing substituted MnP4 .............117
5.3.2 Mn-porphyrins substituted into self-assembled films of
Im O D PA ................................................................................. 124
5.3.3 Self-assembling the MnP4 and ImODPA from a
mixed solution.........................................................................130
5.3.4 Other methods for preparing ImODPA and MnP4 containing
film s ....................................................................................... 131








5.3.5 Characterization of films containing MnP4 and ImODPA
by XPS and ATR-IR..............................................................134
5.4 Conclusions............................................................................................ 141

6 MANGANESE PORPHYRIN AND IMIDAZOLE CONTAINING
ZIRCONIUM PHOSPHONATE THIN FILMS AS CATALYSTS ....................144

6.1 Background ..............................................................................................144
6.2 R esults................................................................................................ 147
6.2.1 Catalysis With PhIO as the Oxidant ............................................147
6.2.2 Catalysis Using H202 as the Oxidant......................................... 159
6.3 Conclusions......................................................................................163

REFEREN CES.......... ......................................... ..................................................164

BIOGRAPHICAL SKETCH ...................................................................................... 171












LIST OF TABLES


Table page

3.1 UV-vis data from symmetric and alternating films of PdP4. Xm is given for
monolayers, and interlayer thickness is given for multilayers of films
transferred under a variety of transfer conditions.......................................... 71

3.2 UV-vis data from symmetric and alternating films ofPdP1. max is given for
monolayers, and interlayer thickness is given for multilayers of films
transferred under a variety of transfer conditions........................................77

6.1 Time dependence of epoxidation of cyclooctene using 40 umol cyclooctene
and 5 jmol PhIO in lmL of solution. To the homogeneous reaction was
added inmol ofM nP ........................................................ ....................151

6.2 Conversion of cyclooctene to cycloctene oxide with 40 pmol cyclooctene
and 5 pmol PhIO in ImL of solution using MnP4 LB film........... ..........154

6.3 Conversion of cyclooctene to cyclooctene oxide with varying cyclooctene
to PhIO ratios in ImL of solution using MnP4 SA films over 24 hr.............155

6.4 Conversion of cyclooctene to cyclooctene oxide with 40 upmol cyclooctene
and 5 pmol PhIO in ImL of solution and in films containing imidazole......157

6.5 Comparison of blanks and homogeneous epoxidation yields in vials vs. in
the reaction cells ....................................... .............. .............................158

6.6 Conversion of cyclooctene to cyclooctene oxide with 400 pmol cyclooctene
and 80 pmol H202 in ImL of solution using imidazole and porphyrin ........ 161














LIST OF FIGURES


Figure page

1.1 Schematic of an isotherm and corresponding monolayer behavior.......................

1.2 Schematic of X-, Y-, and Z-type Langmuir-Blodgett multilayers........................7

1.3 X-ray diffraction diagram ................................................................................... 9

1.4 Illustration of ATR-IR Experiment...................................................... ........ 10

1.5 Schem atic of XPS experiment ............................................................................. 11

1.6 Schematic of polarized UV-vis experimental beam directions............................13

1.7 Behavior of the oblique dichroic ratio versus an orientation parameter (P)..........14

1.8 Crystal structure of zirconium phosphate ......................................................... 17

1.9 Comparison between tradition LB films and metal-phosphonate LB films ..........20

1.10 Schematic of formation of divalent or trivalent metal phosphonate films.............22

1.11 Structures of porphyrin-type molecules A) porphine B) free base
porphyrin, and C) pthalocyanine.................................................................25

1.12 UV-vis spectrum of a metallo-porphyrin (PdTPP)..............................................25

1.13 Outline of 16-member principle resonance structure of metallo-porphyrin..........26

1.14 Gouterman's four-orbital model .......................................................................27

1.15 Transition dipole moments in metallo-porphyrin .............................................30

1.16 Porphyrin chromophore interactions: The square represents the
chromophore and its disecting axes. A) H-type or face-to-face
aggregates; B) edge-to-edge aggregates; C) J-type or head-to-tail
aggregates .............................................. ................................................... 32
1.17 Suggested mechanism of olefin epoxidation catalyzed by MnTPP.....................35










2.1 Schematic of Langmuir-Blodgett trough and monolayer ......................................42

2.2 Schematic of the three-step deposition process used for zirconium
phosphonate film s..................................................................... .....................45

2.3 Schematic of catalysis cell, side view............................................................54

2.4 Schematic of catalysis cell, top view .................................................................55

3.1 Structures of A) PdP4 and B) PdP .......................................................................59

3.2 Schematic of Pd-porphyrin films formed: a) alternating ODPA/Zr/PdP,
b) alternating ODPA/Zr/PdP:ODPA mixed film, c) symmetric
PdP/Zr/PdP, d) symmetric PdP:ODPA/Zr/PdP:ODPA .................................60

3.3 Solution UV-vis of Pd-porphyrins in CHC13: A) PdP4, B) PdP .......................62

3.4 Solution UV-vis of PdP4 in EtOH and water compared to CHC13......................63

3.5 Isotherms of PdP4, pure and mixed with ODPA (PdP4:ODPA), on a
w ater subphase.................. .......................................................... ...........64

3.6 Reflectance UV-vis of PdP4 on water subphase..............................................65

3.7 Isotherms of PdP1, pure and mixed with ODPA (PdP1:ODPA), on a
w after subphase.................................................................................................66

3.8 Reflectance UV-vis of PdPI on water subphase....................................................67

3.9 Reflectance UV-vis of 10% PdP4: 90% ODPA on a water subphase ...................68

3.10 Mean molecular area vs. ratio of ODPA/Porphyrin: A) PdP4, B) PdPI ..............69

3.11 Transmission UV-vis of PdP4 films transferred at high and low MMA.
Absorbance scale corresonds to the film transferred at 300 A2 molecule'1 .....72

3.12 UV-vis of SA PdP4 films rinsed in hot CHC3 ............................................ ....75

3.13 Transmission UV-vis of films of PdP 1 transferred at high and low MMA...........76

3.14 Absorbance of Soret vs. time rinsed in hot CHC13: A) PdP4, B) PdPl ................78

3.15 Illustration of orientation and packing of PdP 1 films transferred at high and
low M M A ................................................................................................. 79








3.16 Illustration of orientation and packing of PdP4 films transferred at high and
low M M A ................................................................................................... 80

4.1 Structures of A) MnP4 and B) MnPO .............................................................84

4.2 UV-vis of M nPO in CHC13................................................................................... 87

4.3 Solvent behavior of MnP4 in water, EtOH and CHC3 ........................................88

4.4 UV-vis concentration study of MnP4 in CHCl3: a) 10-6 M, b) 10-5 M ................88

4.5 MnPO in CHCI3 (1 x 10"7 M) with ethylphosphonic acid: a) pure MnPO,
b) 1 x 104 M ethylphosphonic acid, c) 2 x 104 M ethylphosphonic acid,
d) 3 x 104 M ethylphosphonic acid, e) pure MnP4 .......................................90

4.6 Solution UV-vis investigation of MnP4's sensitivity to displacement of
R-PO(OH)2 by chloride at 1 x 10-5 M. The arrows indicate the changes
in the intensity of the peaks as the chloride concentration changes from
0.0 M to 0.1 M while the concentration of MnP4 stay constant in CHC13 ......93

4.7 Isotherm of MnP4 on water subphase............. .......................................................94

4.8 Reflectance UV-vis of MnP4 on water subphase ................................................95

4.9 UV-vis of MnP4 capping layers transferred onto ODPA/Zr at different
surface pressures (indicated by the arrows)...........................................96

4.10 LB films of MnP4 transferred at A) 15 mN/m and B) 5 mN/m rinsed in
CH C13....... .............. ........................................................ .......................98

4.11 MnP4 transferred by LB at 0.7 mN m'' and rinsed in CH3CN: A)
transferred from a 0.5 mg mL-' solution...................................................99

4.12 MnP4 transferred from 0.1 M [CI-] aqueous subphase at 4 mN m' ..................100

4.13 MnP4 self-assembled from EtOH/H20 and rinsed in CHC13. The legend
indicates the spectra after rinsing, after being left overnight and the
rinsed again over a three day period ....................................................101

4.14 SA MnP4 films with rinsing in hot CH3CN ....................................................102

4.15 UV-vis response of a SA MnP4 film during rinsing with hot CH3CN.............. 103

4.16 UV-vis of MnP4 self-assembled films before and after rinsing in hot EtOH......104

4.17 MnP4 self-assembled from a 0.1 M chloride solution....................................... 105









4.18 XPS of MnP4 SA film. The insert is an enlarged view of the same spectrum
between 200 and 80 eV .............................. .............................................106

5.1 Structures of A) MnP4, B) MnPO, C) ImODPA and D) ImH............................110

5.2 Simplified Schematic of MnP4 and ImODPA incorporation in films................. 11

5.3 Solvent response of A) MnPO and B) MnP4 to ImH...........................................114

5.4 Solvent response of A) MnPO and B) MnP4 to ImODPA. Legends indicate
the molar ratio of MnP to ImODPA ............................................................ 116

5.5 UV-vis of ODPA/Zr/HDPA, SA MnP4 film rinsed in hot CHCl3 .................119

5.6 MnP4 substituted onto ImODPA:HDPA LB films after CHCl3 rinsing .............121

5.7 MnP4 substituted onto a 25% ImODPA/HDPA film, rinsed in room
temperature and hot CHCl3....................................................................... 122

5.8 UV-vis of an ImODPA/ MnP4 film after drying ............................................... 123

5.9 MnPO attached to a 25% ImODPA/HDPA LB film and rinsed in hot CHC1......124

5.10 MnP4 substituted onto a pure ImODPA SA film ..............................................126

5.11 Reversibility of the chloride/phosphonic acid binding ...................................... 127

5.12 MnP4 substituted film rinsed in chloride and t-butylamine solutions...............28

5.13 MnP4 substituted from a 0.1 M Cl- solution onto an ImODPA layer, and
compared to an MnPO solution with ImH binding......................................129

5.14 ImODPA/MnP4 self-assembled from 70/30 mixture and rinsed in hot
C H C 13............................................... ..................................................... 131

5.15 ImODPA substituted into a MnP4 LB film transferred at 10 mN m'' ..............132

5.16 LB film of MnP4/ImODPA transferred from a 25/75 mixture on an aqueous
subphase, pH 11.3...... ............................................................................ ...133

5.17 XPS multiplex scan over the Nis region of A) ImODPA, and B) MnP4 self-
assembled films. The dashed line represents the Gaussian peak fit .............134








5.18 XPS multiplex scan of Nls region of ImODPA/MnP4 film self-assembled
out of 70/30 CH2C12 solution. The dashed lines represent the Gaussian
peak fits.................................................................................................... 136

5.19 XPS multiplex scan of mODPA/MnP4 film self-assembled from a 70/30
m ixture in EtOH/H20 ................................... ............................................136

5.20 ATR-IR of ImODPA SA film............................................................................... 138

5.21 Increase in absorbance intensity of 2918 cm'" peak in ImODPA with
SA tim e ..........................................................................................................139

5.22 ATR-IR ofalkyl region of: A) MnP4 substituted on a 100% ImODPA base
capping layer, B) MnP4 substituted on a 25% ImODPA base
capping layer............................................................................................ 141

6.1 SA MnP4 film before and after 24 hr. catalysis run with 40:5:20
cyclooctene: PhIO:decane in CH2C2 ....................................................148

6.2 SA MnP4 film before and after 2 hr. catalysis run with 40:5:20
cyclooctene: PhIO:decane in CH2C12 ..........................................................149

6.3 UV-vis of MnP4 film SA from chloride containing solution used in
catalysis with PhIO after 6 hr.......................................................................150

6.4 Bleaching of MnPO in homogeneous catalysis reaction with PhIO.....................152

6.5 MnP4 LB film before and after 24 hr catalysis reaction....................................153

6.6 SA ImODPA/SA MnP4 studied with PhIO for epoxidation of cyclooctene .......156

6.7 SA ImODPA/SA MnP4 studied in the epoxidation of cyclooctene
using H 20 2 ................................................................................................... 159

6.8 SA ImODPA/SA MnP4 after rinsing and after 24 hr in catalysis reaction
w ith excess H 20 2........................................................................................ 161

6.9 SA ImODPA/SA MnP4 film with catalysis using 8 .mol cyclooctene
to 0.2 m ol H 20 2 ........................................................................................... 162














Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy


METALLO-PORPHYRIN CONTAINING ZIRCONIUM PHOSPHONATE
THIN FILMS: STRUCTURE AND CATALYSIS

By

Christine Marie Nixon Lee

August 2000

Chairperson: Daniel R. Talham
Major Department: Chemistry

Thin films containing mono- and tetra-phosphonic acid palladium tetraphenyl

porphyrins and tetra-phosphonic acid manganese tetraphenyl porphyrins, PdP1, PdP4,

and MnP4, were prepared by both Langmuir-Blodgett (LB) and self-assembly (SA)

techniques. Within the hydrophilic regions of these films was incorporated a

zirconium phosphonate network which lent significant stability and flexibility of

preparation to these films.

In the LB films of the palladium porphyrins, it was found that the mono-

phosphonic acid porphyrins aggregated under all film preparation conditions and in

solutions at high concentrations. However, the chromophore aggregation could be

controlled in the tetra-phosphonic acid porphyrins when the films were transferred at

mean molecular areas greater or near the mean molecular area of the chromophore

itself. Self-assembling the PdP4 was another means of controlling the chromophore








interaction in the films. Because chromophore aggregation was expected to inhibit

catalysis, film preparation conditions were sought in order to avoid this.

LB and SA films of pure manganese porphyrins were successfully prepared by

a number of different methods. Aggregation appeared insignificant when transferred

at high mean molecular areas and when the films were self-assembled. The pure

manganese porphyrin films were successful at catalyzing the epoxidation of

cyclooctene using iodosylbenzene as the oxidant.

To activate the porphyrin for catalysis with peroxide oxidants, a heterocyclic

ligand was also incorporated into the manganese porphyrin containing films. The

heterocyclic ligand used was an imidazole substituted with an octadecylphosphonic

acid chain. Both the manganese porphyrin and the imidazole amphiphile were

tethered to a zirconium phosphonate network, first for ease of film synthesis and

second, to stabilize the film for use in the catalysis reactions.

Though significant catalyst degradation has been reported in homogeneous and

alternative heterogeneous catalysis studies, the manganese porphyrin and imidazole

containing zirconium phosphonate films were generally more resistant to degradation

under catalysis conditions. The stability of the films toward epoxidation conditions

has led to easily recyclable catalysts.













CHAPTER 1
INTRODUCTION


1.1 Ultrathin Films



The study of ultrathin films, especially monomolecular thick films, enables the

study of two-dimensional systems and allows the simplification of complicated

thermodynamic behaviors. Recent interest in monolayers and multilayers focuses on

the many potential applications of organized and functional thin films, which include

optoelectronics,1-3 coatings,4-7 chemical sensors,1,6,8-10 and heterogeneous

catalysts.ll-13 In order to prepare these organized and essentially two-dimensional

structures, the Langmuir-Blodgett (LB) and self-assembly (SA) techniques have been

developed.

The study of monolayer thick films began long before the early twentieth

century investigations of Irving Langmuir and Katharine Blodgett. It is believed that

centuries ago drops of oil were used to calm waves in ponds and other small bodies of

water.14,15 Benjamin Franklin studied monolayers of oil on the surface of a pond.

Agnes Pockels pioneered the study of a monolayer on the water surface in the

laboratory environment, and is credited with building the first trough.15 However, the

first systematic study of monolayers of amphiphilic molecules on aqueous surfaces

began with Irving Langmuir's studies at GE Laboratories and, hence his name is

associated with a fundamental method of preparing organized, monomolecular thick





2


films.16 His associate, Katherine Blodgett first transferred these films from the water

surface onto solid supports.17

The SA technique was first described in scientific reports in the late 1940's and

mid 1950's.18,19 This technique relies on surface-active molecules and the appropriate

surface being placed in contact with one another through a solvent medium. The films

prepared by this method tend to be more stable than traditional LB films because of

the types of surface interactions that drive their formation.

The traditional LB technique employs different surface interactions depending

on the method of transfer. First, as in the case of hydrophilic-hydrophilic transfers of

neutral amphiphiles from a pure aqueous subphase, the interactions are primarily

hydrogen bonding in nature. Ionic bonding is commonly observed in the case of

hydrophilic-hydrophilic transfers from a metal ion-containing subphase. In the case of

hydrophobic-hydrophobic transfers, van der Waals interactions are involved. During

LB depositions, the film is usually physisorbed to the surface implying some through-

space interaction, while in SA films, the molecules are adsorbed to the surface through

a chemical bond. The SA method relies on the formation of covalent bonds between

the surface-active component of the molecule and the solid substrate often resulting in

more stable films.20

In LB films, the hydrophilic head group typically dictates the area the molecule

fills in the interfacial region. The alkyl groups, therefore, adjust to maximize the van

der Waals contacts leading to organized packing within this region.21 Unfortunately,

control over the film packing and organization achieved by the LB technique is absent

in the SA method. The molecular organization in SAMs (self-assembled monolayers)

is dictated solely by the geometry of the active sites on the surface. However, in LB

films, the pressure and area of deposition can be selected to deposit a particular phase

of the monolayer and to influence the transferred film organization. An understanding









of the mechanics of both the LB and SA processes is important in appreciating thin

film research and its application to many areas of science.20


1.1.1 Langmuir-Blodgett Films and Characterization

.1.1.11 Langmuir monolayer formation: the isotherm. The Langmuir

monolayer is achieved by placing droplets of an amphiphile solution, in a volatile

solvent such as CHC13, on the aqueous subphase in such a way as to uniformly spread

the compound on the surface. Typically, the presence of an amphiphile works to

decrease the surface tension, and the difference is defined as the surface pressure. In

Equation 1.1, H is the two-dimensional surface pressure typically measured in mN m1,

Yo is the initial surface tension of the subphase and yf is the surface tension of the

subphase and film.22,23



n = o Y(1.1)


The record of the monolayer formation on the water surface, the I vs. area (A)

isotherm, depends on the change in the surface pressure with a change in the mean

area per molecule (MMA) on the surface.15,22 The surface pressure is measured using

a sensitive microbalance, such as a Wilhelmy balance, while the area is computer

controlled using movable barriers, which define the monolayer boundaries.

Upon room temperature spreading, the monolayer is at a very low density and

behaves like a two-dimensional gaseous phase (Figure 1.1). In this phase, the

molecules are theoretically not in constant contact with one another, although

aggregation may occur depending on the affinity of the amphiphilic molecules for one
another. There are random collisions, but there is no appreciable increase in surface









pressure because, in effect, there is not a true monolayer, and the presence of the

amphiphile has virtually no effect on the surface tension of the subphase.20 There is

some debate on the existence of a two-dimensional gaseous state; some researchers

claim that there is always aggregates formed, which interact within the gaseous

phase.23

As the monolayer is compressed, the molecules will come in contact with one

another, and an observable rise in H occurs. In the initial region of noticeable pressure

increase, the molecules are colliding, but the film is in a fluid-like state. The

molecules have no long-range orientational order and they are not close-packed or

organized. This region is often called the liquid-expanded state (LE) (Figure 1.1).

Within the LE phase, the alkyl chains have many degrees of freedom, and gauche

conformations are observed within the chains.

The further compression of long chain fatty acid amphiphiles leads to a more

crystalline and organized monolayer. In this phase, the hydrophobic tails of the

amphiphiles adopt an overall orientational order that is maintained within the film

domains. This orientational order seeks to balance the van der Waals interactions

between the alkyl chains with the pressure applied by the barriers. Within this region,

referred to as the liquid-condensed phase (LC) (Figure 1.1), the slope of the isotherm

is very steep, meaning that the pressure goes up rapidly without much change in the

MMA. In some cases, the structure of the amphiphiles may prohibit the formation of a

close-packed monolayer regardless of the pressure, and therefore, the monolayer enters

and remains in the LE phase.15

When the monolayer cannot compress any further, additional applied pressure
from the barriers causes the monolayer to fold either over or under itself forming

collapsed regions. The collapse point is identified as the first point of deviation from

the linear slope of the LC region of the isotherm. 15,22















C. Liquid Condensed State



E

E- *** *.

B. Liquid Expanded State


\ F L-* -
A. Gaseous State




MMA (A2 molecule-1)



Figure 1.1: Schematic of an isotherm and corresponding monolayer behavior.


1.1.1.2 Langmuir monolaver characterization: creep and hysterisis tests and
reflectance spectroscopy. Although the isotherm is very important in identifying the

general behavior of a monolayer film, it does not give specific information about such
things as the monolayer stability, alkyl chain orientation, or aggregation of the
amphiphiles. These more specific ideas of monolayer behavior can be discerned from
experiments such as creep and hysterisis tests, reflectance UV-vis, fluorescence

microscopy, Brewster angle microscopy, and surface potential measurements,23 to









name a few.15,22 The methods applying to the films discussed in this dissertation will

be described here.

Creep tests provide information on monolayer quality and can be recorded in

two ways. First, the monolayer is compressed to a certain pressure and then that

pressure is maintained by the barriers expanding or compressing as necessary while

recording the change in area with time. Second, the monolayer is compressed to a

defined area, which is maintained by stationary barriers, and the pressure is monitored

over time. Stable monolayers will show a static surface pressure or little movement in

the barriers after the desired pressure is reached. Unstable monolayers go through

constant and sometimes drastic rearrangements, which force contraction or expansion

of the barriers. For example, the hydrophobic nature of the amphiphile may be

insufficient and the amphiphile may dissolve into the subphase forcing the barriers to

compress to maintain nI. Also, the vapor pressure of the amphiphile may lead to their

evaporation, causing the surface pressure at constant area to decrease or the barriers to

move forward to hold constant pressure in proportion to the instability of the film.

Alternatively, the amphiphiles may have a strong affinity for one another, leading to

agglomeration and either causing an anomalous change in the surface pressure at

constant area or forcing the barriers to work to maintain the surface pressure.22

Hysterisis studies monitor the effect of the monolayer stability on the

reproducibility of the isotherm upon compression and decompression. If the

amphiphiles tend to aggregate, the isotherm will not retrace its compression curve in

its decompression cycle. From creep tests and hysterisis experiments, the ability of

the monolayer to hold its form and to possibly be transferred can be ascertained.24

Reflectance UV-vis spectroscopy is used to understand the optical behavior of
monolayers of chromophore-containing amphiphiles on the water surface. One

method for studying the Langmuir monolayer by reflectance UV-vis involves placing









a mirror on the base of the trough and reflecting a beam through the monolayer onto

this mirror, and back into a detector. These studies can help determine the onset of

aggregation in films with such a tendency.25,26

1.1.3 Langmuir-Blodgett film formation. LB films are formed by vertically

transferring Langmuir monolayers from the water surface onto a solid support. There

are three common vertical dipping techniques, which form X, Y, and Z-type films

(Figure 1.2). 15,23 In X-type LB films, a Langmuir monolayer is transferred onto a

hydrophobic substrate in such a way as to maintain head to tail type interactions. In Z-

type LB films, the monolayer is transferred onto a hydrophilic substrate also forming

head to tail interactions. X- and Z-type films can be prepared on a specially designed

trough, which allows one stroke to be made through a monolayer and the next to be

made through a clean subphase. However, some amphiphiles have a preference for

this type of interaction and upon regular dipping, these structures form spontaneously.

Y-type multilayers are most common and can be prepared on either hydrophilic or

hydrophobic substrates. Y-type multilayers are typically the most stable due to the

strength of the head-head, tail-tail interactions.15


t --- --- --]-- -tp
0 ----[. ---
----- -- X-type

---0---0
-0 e----- --O
_---- ---* Z-- Z-type
S- ~- --

---- -- --O

SFigure .2: h YoX-type

Figure 1.2: Schematic of X-, Y-, and Z-type Langmuir-Blodgett multilayers.











1.1.1.4 Langmuir-Blodgett film characterization. The quality of the transferred

film is first indicated by the transfer ratio, which is a measure of the change in the area

of the monolayer versus the area of the substrate coated by the monolayer. A transfer

ratio of unity indicates that the monolayer is transferred with the same area per

molecule that it had on the water surface. This "perfect" transfer ratio assumes that the

monolayer on the water surface was stable and was not reorganizing significantly

during transfer. A consistent deviation from unity could imply a change in

organization upon transfer; however, if the transfer ratio is irregular, the transferred

film is probably poor quality.15

There are many analytical techniques used to study transferred films. Film

characteristics typically of interest are thickness, interlayer spacing, molecular

orientation and packing, film coverage, surface topology, chemical composition, and

optical and magnetic properties. The techniques used to study these parameters are

well described in the literature.20

X-ray diffraction is a reliable technique to probe interlayer spacing, and from

interlayer spacing, film thickness can be inferred. The X-rays are essentially reflected

from planes of higher electron-density. The interaction of X-rays with the crystalline

planes can be described by Bragg's law (Equation 1.2):



nA = 2dsin0 (1.2)


where n is an integer, X is the wavelength of the radiation, d is the interlayer spacing,

and 8 is the angle of incidence and reflection of the beam.27

Ideally, there should be a significant difference between the electron density of

the head group and that of the hydrophobic region allowing X-ray diffraction peaks to







be observed in LB films. The d-spacing, which quantifies the periodicity between
planes of high electron density, therefore, is the measure of the distance between head
groups. This technique is very sensitive to long-range periodicity, and many narrow
001 peaks are typically indicative of a well-defined layered architecture (Figure 1.3).23





S I 1O
A- .. .. ... f


${UTTT1TTTTW
L1


d-spacing


Figure 1.3 X-ray diffraction diagram.

To study the chemical make-up of the surface, attenuated total reflectance
FTIR (ATR) and X-ray photoelectron spectroscopy (XPS) are employed. ATR studies
involve transferring a film onto a crystal, such as parallelogram-shaped germanium or
silicon crystal with ends cut at 450 angles. This is an ideal method for recording the IR
spectra of films because it allows the film to be sampled many times due to the
internal reflection of the IR beam through the crystal. ATR also provides information
about the surface coverage and packing modes. Further, polarized studies using this
technique can give information about the film organization and orientation (Figure
1.4).15 Background information pertaining to films studied by ATR-IR, allows


^








elucidation of information about films containing new amphiphiles. For example, by
comparing the areas of the alkyl stretches of a new amphiphile to that of well-
understood fatty-acid films, an idea of the transfer quality can be obtained. This tool
is particularly helpful in studying monolayers with transfer ratios varying from unity.
ATR-FTIR can also indicate the packing nature of the alkyl chains. If the
chains are in a mostly trans configuration and close-packed, the asymmetric CH2
stretch (vCH2) will occur at 2918 cm-1 and have a full width at its half maximum
(FWHM) of ca. 20 cm-1. The symmetric CH2 stretch (v,CH2) will occur at ca. 2852
cm-1. If there are a significant number of gauche interactions in the chains, the v,CH2
and vCH, stretches will shift to higher energies (ca. 2924 cm-1 for the vCH2 and ca.
2856 cm-1 for the v.CH, stretches).28,29





^11L1 LMM


11111 111111111 I beam

Figure 1.4: Schematic of the ATR-IR Experiment.


XPS is a method used to determine the elemental make-up, and possibly,
atomic proportions within a film based on the photoelectron effect. XPS measures the
energy of an expelled electron as the surface is bombarded with a monochromatic X-
radiation source (Figure 1.5). When a high-energy source is applied, the kinetic energy


WTW- "
A A








of the emitted electrons can be related to the excess energy and to the strength of the

electron's binding by Equation 1.3, which is the Einstein photoelectric law:27



Ek, = hv e- E, (1.3)


where Eb is the binding energy, e is the charge of the electron, h is Planck's constant, v
is the frequency of the radiation, and <) is the work function corresponding to the
minimum energy required for ejection of an electron.

4 Detector
Ek = hv- Eb
Monochromatic X-ray
Beam
e






Figure 1.5: Schematic of XPS experiment.

The XPS spectrum plots electron counts versus binding energy. Binding
energies are unique to each element present in the film, as well as to that element's
chemical environment and oxidation state. Therefore, from a scan over a wide range
of binding energies, called a survey scan, XPS results can be used to define the
elements present in the sample. A more extensive scan, or a multiplex scan, over a
narrow range of binding energies can clarify peak splitting, which can be assigned to a
change in the chemical environment or oxidation state. Offord, et. al., in their study of
a Ru-porphyrin linked to a thiol on gold SA film containing a percentage ofimidazole
terminated thiol surfactants, observed two peaks within the N,, region of the XPS









spectrum. These two peaks were associated with the different nitrogen environments

in the imidazole and porphyrin, clearly indicating that both species were present in the

mixed film.30

The intensities of the XPS peaks can be used to determine the relative ratios of
the elements present, and can indicate the type of crystalline lattice formed. However,

the intensities of the XPS peaks are sensitive to many parameters such as the element's

electron escape depth, which can complicate the determination of the elemental ratios.
In a given sample, the observed relative peak intensities are compared to a calculated

value based on Equation 1.4:




-dP ^
I;fexp d.
I1 = (si (1.4)
IA / exp + /;I exp[ -- +...
,,A(sin) A,,(sin 0)


where IA is the relative intensity of element A, IA' is the atomic sensitivity factor, d. is

the overlayer thickness, 0 is the incident angle of the X-ray beam, and %, is the

inelastic mean free path. The inelastic mean free path represents the distance over

which 60% of the electrons can travel before inter-electron collisions lead to a loss of

energy31 and is defined by:32



,e = 10[49/(Ekin 2)+0.11(E o)05] (A) (1.5)



UV-vis spectroscopy reveals a film's optical behavior. Typically, films are
transferred onto glass or quartz substrates and transmittance studies are performed.









Using polarizers and stages that allow careful placement of the substrates at different

angles of incidence to the beam, the orientation of the chromophores within the films

can be determined. By comparing the absorbance intensity in the s- and p-

polarization, a dichroic ratio can be calculated using Equation 1.6:




A
P


Orientational order within the plane of the film and substrate is obtained by looking at

results from 0" and 90 (s and p) polarization as the beam is normal to the surface (0

angle of incidence). Studying the polarization at higher angles of incidence (typically

450) enables the determination of the orientation out of the plane (Figure 1.6).



o0 polarization


> 9 polarization






450 orientation
Qo orientation


Figure 1.6: Schematic of polarized UV-vis experimental beam directions.










The dichroic ratio can be used to determine the chromophore orientation in a

film. In the case of films containing porphyrin chromophores, Orrit et al. determined

that the dichroic ratio can be translated into an orientation parameter (P) using the

graph shown in Figure 1.7,25 and hence, an orientation angle (0) can be established

using Equation 1.7:


P=(cos2 0)


(1.7)


0 represents the angel between the surface normal and the chromophore's molecular

plane. As is often observed within the plane of a film containing porphyrins, if D is

unity, there is no preferred orientation. If D = 1.5, P = 0 and therefore, 0 = 90 as

measured from the surface normal.




I I I I I

1.5 1: A,= 0.2%
S3 2: A= 5%
3: A,= 10%
4: A, = 20%
5: A = 50%
1.0 5



0.5

S= 450


0.0 0.2 0.4 0.6 0.8 1.0
Orientation Parameter (P)

Figure 1.7: Behavior of the oblique dichroic ratio versus an orientation parameter
(P).25









Porphyrin containing films often have oblique dichroic ratios of approximately

1.5, corresponding to the chromophores lying parallel to the substrate. For example,

Zhang et al., obtained such a result in LB films containing a free base tetraphenyl

porphyrin either pure or mixed with stearic acid, where the porphyrin was the

hydrophilic head group with long alkyl substituents.33


1.1.2. Self-Assembled Films

Zisman introduced SAMs to the literature little more than 50 years ago. His

studies involved self-assembling long-chained alcohols onto a glass surface using

hexadecane as the inert solvent.18 This study showed that films prepared in this

manner had wetting properties similar to those seen in films prepared by the LB

technique.

Sagiv et al. studied octadecyltrichlorosilane (OTS) on hydroxylated surfaces,

such as glass, to form a siloxane polymer. Multilayers were produced if the

amphiphile was terminated at both a and o positions by surface-active groups.15,34

When a and co positions were two different functionalities, subsequent dipping in self-

assembly solutions produced non-centrosymmetric films. Unfortunately, studies have

shown that small defects in the early layers can magnify upon multilayer formation

such that nearly all order breaks down by the tenth layer.20 The SA of OTS is now

commonly used for hydrophobisizing glass slides for LB substrates.

The chemisorption ofthiols on gold was initiated by Nuzzo and Allara35 and

continued by Porter,36 Whitesides,37 and others. Alkyl thiols, in which the chain

lengths range from one carbon to over twenty, have been studied. Closely packed

layers were observed when the chain length exceeded eleven carbons.36 The gold

surface used in these studies was formed by vacuum evaporation onto cleaved alkali-









metal halide surfaces.37 Many of the surfactants studied by self-assembly did not form

stable monolayers on aqueous subphases, and therefore, could not be studied by the

LB method. However, these surfactants were easily studied by the SA method.


1.2. Hybrid Organic/Inorganic Ultrathin Films Based on Layered Solids


1.2.1. Background

A new class of LB films has been developed, which incorporate an inorganic

metal phosphonate network into the polar region.28,38-41 These films, which can

contain a variety of organic groups and metals, were inspired by and show analogous

behavior to their solid-state metal phosphonate analogues. In addition, these films are

more stable than typical fatty-acid based LB films, and the inorganic lattice provides

potential function.42

The metal phosphonate solid-state materials are attractive because they can be

prepared at low temperatures from aqueous solutions. Further, the structures can

provide a model system to which the film properties can be compared Due to the

structure of the metal lattices, which directs the film formation, the orientation and

packing of the alkyl region is predictable.

Metal phosphonate materials are especially interesting due to their potential

applications in the areas of sorbents43 and catalysts,44 and because of their layered

structures, these materials can be used as intercalation compounds.45-49 The interest in

the metal phosphonates was sparked by their potential as inorganic ion exchange

materials;50-52 however, the organic region can also be modified and functionalized,

providing a straightforward method for preparing a wide variety of materials.









1.2.1.1. Zirconium Phosphonate solids. Clearfield published early work on

metal phosphonates and phosphates in the 1960's.53 The focus at this time was on the

zirconium solids which form two preferred phases, a and y, which have the

compositions Zr(HPO4)2-H20 and Zr(P04)(H2P04)-2H20, respectively. In these

layered materials, a two-dimensional metal lattice is formed and separated from an

adjacent metal lattice by the organic layer in the phosphonates or by the hydrogen

bonds from the fourth hydroxy site in the phosphates. The interlayer area in these

solids forms a possible domain for intercalation of inorganic materials such as

amines.53


OH OH OH OH






OH OH OH OH
OH OH OH OH





OH OH OH OH
0 Z,

0 P
O o

Figure 1.8: Crystal structure of zirconium phosphate.53



The crystal structure of the Zr-phenylphosphonate solid was determined in the

1980's and found to form a structure similar to the a-phase. Subsequent studies

revealed that any alkyl or aryl group whose area was under 24 A2 would form an

identical metal lattice structure while only the interlayer distance changed. In the n-









alkyl phosphonates, it was found that there is a tilt angle in the chains of between 550

and 600. This tilt allows for maximization of the van der Waals forces between the

chains even within the solid-state materials. Though the structures formed are dictated

by the geometry of the inorganic lattice, the hydrophobic region does rearrange to

balance these strong forces with the maximization of their overlap.53 A change in the

organic group can lead to very different structures and properties of the solids. Bulkier

groups may form new crystal structures or have three-dimensional metal lattice

formation. Also, the different organic groups can impart different function to the

films.

1.2.1.2. Divalent and trivalent metal phosphonate solids. After extensive

research on the zirconium phosphonate solids, interest branched to divalent and

trivalent metal phosphonates. The poor solubility of the zirconium phosphonate solids

in most standard solvents meant achieving single crystals was difficult; therefore, most

of the crystal structure data was achieved from powder X-ray diffraction patterns.

However, di- and trivalent metals tend to be soluble in acidic solutions, allowing

single crystals to be obtained by slowly changing the solvent pH or the metal ion

concentration.

Metal phosphonate materials have been prepared with a variety of different

divalent metals such as Mg2+, Mn2, Zn2+, Ca2, and Cd2+.54-56 From the crystal

structures, it was determined that the composition of the divalent series metal

phosphonates is M"(O3PR)'H20 for Mg, Mn, Zn, Ca and Cd. In these materials,

layers of the metal atoms are octahedrally coordinated by five phosphonate oxygens

and one water molecule, with each phosphonate group coordinating four metal atoms

making a cross-linked M-O network. A second structure, the orthorhombic

MII(HO3PR)2, was observed for the Ca phosphonates. A structural exception to the









above divalent series is Cu(II).48,57 The Cu atoms in these phosphonate materials are

five coordinate and form a distorted tetragonal pyramidal geometry.

Mallouk has prepared a series of lanthanide phosphonates. The structure of

these materials is given as Ln(III)H(O3PR)2, where Ln represents La, Sm, or Ce. The

lanthanide-series phosphonates are more soluble than the zirconium solids, but less

soluble than the divalent materials. Therefore, single crystal data was not easily

obtained.58,59

ATR-IR provides a facile method for characterization of the metal phosphonate

lattice formation. Vibrational modes assigned to the phosphonate are extremely

sensitive to the mode of metal binding. Thomas et al. have assigned the va(CH2)

vibrational frequencies for the divalent metal-phosphonates to be in the range of ca.

1050 1100 cmn' where the v,(CH2) stretches occur ca. 970 990 cmn'.60 Each metal

phosphonate material has characteristic stretches in these regions.


1.2.2. Self-Assembled Films Incorporating Metal Phosphonate Binding

After Sagiv's work with self-assembling films of octadecyltrichlorosilane

(OTS), it seemed a natural step to translate the formation of the thermodynamically

stable and insoluble layered metal phosphonate solids into ultrathin films. Self-

assembly was the first technique employed to produce metal phosphonate thin films.

Mallouk and coworkers formed the metal phosphonate self-assembled films by first,

exposing a silicon or gold surface to an appropriate template forming alkyl-mercaptan

that was substituted with a terminal phosphonic acid.61,62 This phosphonic acid was

active toward the metal salt solution in which the substrate was then dipped. After

metallating the surface, the substrate was dipped in a solution of an a, co-

bisphosphonic acid, which left another phosphonic acid on the surface to be









subsequently metallated, and the cycle continued until multilayered films were

fabricated.

The self-assembly of metal phosphonate films is made possible by a very
strong attraction between certain metal ions, particularly the tetravalent metals such as

Zr4, for the phosphonate groups of alkyl phosphonic acids.61-63 However, the
individual metal salts and the phosphonate are themselves soluble. This particular

affinity between metal and phosphonate, makes possible the formation of

monomolecular layers during each step of the cycle and the ability to assemble

controlled multilayers.


1.2.3. Metal Phosphonate Langmuir-Blodgett Films

Two methods of film formation have been employed to incorporate the metal
phosphonate lattice into the polar region of LB films, one for the divalent and trivalent
metals which are soluble in acidic media, and one for the tetravalent and some

trivalent metals which are insoluble even at low pH. A schematic comparing

traditional LB films to metal-phosphonate LB films is shown in Figure 1.9.



Hydrophobic
A., region

Polar
region MM
Metal
phosphonate
region
A B

Figure 1.9: Comparison between A) traditional LB films and B) metal-phosphonate
LB films.









The zirconium metals have such a high oxophilicity for the phosphonate

oxygens, that when a phosphonic acid amphiphile is spread on the surface of a

zirconium cation containing aqueous subphase, the monolayer crystallizes before it

can be transferred. Therefore, a three-step deposition procedure has been developed.

A phosphonic acid containing monolayer is formed on the surface of a pure water

subphase and transferred onto a hydrophobic substrate. Onto this phosphonic acid

surface, a layer of zirconium is assembled, followed by the transfer of a second LB

monolayer containing a phosphonic acid. This three-step deposition technique will be

described in detail in Chapter 2.28,38

Advantages of this three-step technique include the fact that at the hydrophilic

stage, the monolayer is stable and can be independently characterized by ATR-FTIR

or XPS, etc. Second, this method allows the formation of alternating films in which

the template and capping layers do not have to be formed of the same amphiphile. The

option of forming alternating films is important because some amphiphiles do not

transfer on the down stroke but will transfer onto an ODPA template layer. A

disadvantage of the three-step deposition of the phosphonate films occurs at the self-

assembly of the zirconium lattice. The self-assembly of the zirconium onto the ODPA

template causes the metal phosphonate lattice to be amorphous, whereas in a one-step

deposition, the metal lattice is crystalline.

An alternative technique of film formation is employed for the divalent and

trivalent metals.41 In these cases, the metal salts are dissolved in the aqueous

subphase, the phosphonic acid monolayer is formed on the surface, and the

hydrophobic substrate is dipped down and then up through the same compressed

monolayer forming a complete metal-phosphonate layer or an LB bilayer. The

crystallization of the metal-phosphonate lattice occurs on the slow upstroke of the film

through the monolayer (Figure 1.10).








In the one-step method, the pH of the subphase is as crucial to successful
lattice formation as it is in the formation of the solids in aqueous solutions. If the pH
is too high, the affinity of the metals for the deprotonated phosphonates will be too
high and crystallization of the lattice will occur in the Langmuir monolayer rather than
upon transfer. As with the zirconium films, these films will be too rigid to be
successfully transferred.



'M=f

i 11..4 11iiui







--oO e--- --Oo*-








Figure 1.10: Schematic of formation of divalent or trivalent metal phosphonate films.


If the pH is too low, the phosphonate will remain completely protonated, and the films
will transfer without metal binding. Fortunately, the pH effects on the crystallization
of the monolayer have signatures in the isotherm behavior.64 When the pH is too high,
the rigid monolayer gives an erroneous but characteristic isotherm that has a much









higher onset and shallower incline. We believe this isotherm behavior is due to the

rigid films causing deflections in the Wilhelmy balance rather than showing an

increase in surface pressure.


1.2.4. Dual-Function Langmuir-Blodgett Films

After the extensive characterization of simple alkyl metal phosphonate LB

films, there was interest in incorporating function into the organic region that might be

paired with properties in the inorganic lattice to form a "dual function" LB film. As

models, phenoxy and biphenoxy alkyl phosphonic acids were prepared, and divalent,

trivalent, and tetravalent metal phosphonate films were studied. 65,66 Additionally,

films containing azobenzene-derivatized phosphonic acid amphiphiles were

synthesized, and metal phosphonate films were formed also with divalent, trivalent,

and tetravalent metals.67 These results prove that larger organic groups can be

incorporated into the metal phosphonate LB films while maintaining the integrity of

the inorganic lattice structure.

Potential applications of dual functional metal-phosphonate thin films include

magnetic switches, in which the magnetic behavior of the inorganic lattice can be

altered by a structural change in the organic region. Also, films containing a

conductive or non-linear optic organic region as well as a magnetic inorganic lattice

could act as a sensor. This dissertation will focus on the preparation ofporphyrin

containing zirconium phosphonate films where the metal phosphonate lattice acts to

stabilize the films toward potential catalytic reaction conditions.











1.3 Background on Porphyrins


1.3.1 Optical Behavior of Porphyrins

Porphyrins are a common research focus in physics, chemistry, and biology.

Physical and chemical interest in porphyrins stems, for example, from their highly

conjugated structure that allows facile electron-transfer,68-72 and from their chemical

activity at an exposed metal that may be active toward catalysis or chemical

sensing.1,8,73-75 Biologists and biochemists are interested in the common biological

building blocks that are based on the porphyrin structure.76-78

The core structure of the porphyrin is the completely saturated porphine

macrocycle (Figure 1.11).79 Upon reducing this macrocycle to the unsaturated form,

the porphyrin chromophore is achieved. By hydrolyzing one of the pyrrole units, the

chlorin compound is prepared. Another important structure based on the porphine

core is the phthalocyanine or the tetraazatetrabenzporphyrin. Each of these structures

includes either two protons, as in the free base porphyrin, or a coordinated metal

within the center of the porphyrin, called the metallo-porphyrin. Examples of

biologically active porphyrins include chlorophyll, which is a manganese-coordinated

chlorin molecule, and heme, which is an iron-substituted porphyrin.













NH HN N, N N,
HH / N HH N
NH HN N N N 'N



A B C
Figure 1.11: Structures of porphyrin-type molecules A) porphine B) free base
porphyrin, and C) pthalocyanine.


Porphyrins have characteristic and strong optical transitions by which they can

be identified. The bands often observed in visible spectra ofporphyrins include the B

or Soret Band and Q Bands, as seen in Figure 1.12 for a palladium

tetraphenylporphyrin (PdTPP). The Soret Band is associated with the allowed n n*

transition and is typically seen between 380 and 420 nm.80



2.0

Soret (B) band
1.5


1.0 -
A


Wavelength (nm)


Figure 1.12: UV-vis spectrum of a metallo-porphyrin (PdTPP).











The Q-Bands are observed between 500 and 600 nm. The lower energy Q-

Band (Qn) is associated with the electronic origin, Q(0,0) of the lower energy singlet

excited state. The higher energy Q-Band (Qp) has a contribution from a vibration

mode and is denoted Q(1,0). Both Q(0,0) and Q(1,0) are quasi-allowed transitions

with relatively low absorbance intentisties. The Q-Bands are highly sensitive to the

symmetry of the molecule. In porphyrins of D4, symmetry such as metalloporphyrins,

or the diacidic or dibasic forms of the porphyrin, two Q Bands are observed as

pictured in Figure 1.12. The free-base porphyrin is of D2, symmetry and the

degeneracy of the Q-Bands is disrupted, splitting the Q-Bands into four peaks.80

The above described transitions are due to the porphyrin i-electrons and are

n-n* in nature. If these transitions are unperturbed by the central substituent, the




N N
M
N N Q B




Figure 1.13: Outline of 16-member principal resonance structure ofmetallo-
porphyrin.

porphyrin is classified as "regular". Similarly, the emission spectra of regular

porphyrins are determined solely by the chromophore itself. The above explanation of
the UV-visible behavior of porphyrins is based on the free-electron model, in which

the core of the porphyrin, the 16-member heterocyclic, conjugated ring behaves like a

free-electron wire (Figure 1.13). Another popular theory is Gouterman's four-orbital









model (Figure 1.14), which combines the Htickel-MO theory with the free-electron
model. In this model, Gouterman describes four orbitals, two LUMOs, c,(eg) and c2

(eg) each with five nodes, which are degenerate in energy, and two HOMOs, b,(a2.)
and b2(a,), each with four nodes, which are not degenerate. According to the four
orbital model, the Soret Band corresponds to the transition from the lower energy a,.
orbital to the eg orbital, giving a higher energy transition. The Q-Bands arise from the
transition from the a2 orbital, which is higher in energy giving a lower energy

transition.25,80



Cl(eg) 2(eg)













bi(a2u)
....., 2(ale


^ / ^---- -^ j -- -- ---------
% ,

,i "----------. "''-:----...--(--u'---

!'

I? --


Figure 1.14: Gouterman's four-orbital model.









However, there are also "irregular" porphyrins. Irregular porphyrins, typically
metalloporphyrins, are broken down into categories called hypso- and hyper-

porphyrins. In the case of irregular porphyrins, the central metal contains partially
filled shells, which introduce a possibility of metal electrons mixing with porphyrin 7-

electrons. This mixing is caused by the possibility of metal to porphyrin back-binding

due to similar energies of the metals d-orbitals and the porphyrin's n-orbitals. The

central metal ion can lead to significant changes in the optical and emission spectra.

The metal and its oxidation state determine which category the porphyrin's optical

behavior will fall into. Also, the release of electron density from the metal to the

porphyrin enables the metal to stay co-planar with the chromophore as the effective

size of the metal is reduced.79

Hypsoporphyrins have central metals of groups eight through eleven with
configurations d" where m = 6 9 and have filled eg(dn) orbitals. The inclusion of

these metal ions is often associated with a bathochromic or blue shift relative to the

corresponding free base porphyrin. Common hypsoporphyrins include Ni(II), Pd(II),

and Pt(II)-porphyrins. The Ni(II) porphyrins are easily affected by basic axial ligands,

whereas Pd(II) and Pt(II) are typically four coordinate and appear insensitive to the

potential ligand environment 80,81

The second class of irregular porphyrins is called the hyperporphyrins, which
is further broken down into subclasses called p-type, d-type, and pseudonormal

hyperporphyrins. Most metallo-porphyrins classified as hyperporphyrins have central
metals with easily accessible lower oxidation states. Of these, Mn(III) and Fe(III) are
the most well studied due to their biological implications. The spectra of

hyperporphyrins exhibit the Soret and Q-Bands as before with some possible shifting.
Additional prominent absorption bands may be seen typically at higher energies
relative to the Soret Band. The hyperporphyrin spectra demonstrate the effects due to









metal-ligand charge transfer (MLCT) mixed with the porphyrin r-nt* transitions even

within the Soret Band. The MLCT Bands can be porphyrin to metal, metal to

porphyrin, or even axial ligand to metal. Due to the spectral sensitivity to
chromophore substituents, to the metal its oxidation state, and to the nature of the axial

ligand, and the additional UV-vis Bands, hyperporphyrin spectra are much more

difficult to analyze.80,81

The d-type hyperporphyrins include metals of groups six through eight.

Mn(III)-porphyrin, for example, is d4 and S = 2, or high-spin, and is a characteristic d-

type porphyrin. In chloroform, Mn(III) tetraphenylporphyrin shows six peaks. An
early researcher of the Mn-porphyrins, Boucher, termed these peaks by Roman

numerals going from low to high energy. The first two peaks are in the far-red region

between 800 and 650 nm. Bands III and IV absorb in a region similar to the Q-Bands

in regular porphyrins, between 500 and 650 nm. Band V is similar to and often called

the Soret Band though this band now includes contributions from metal to ligand

mixing. Band VI is typically around 350 nm. The ratio of Bands V and VI is very

sensitive to axial ligands and ring substituents. These bands are due to porphyrin to

metal charge transfer a,,(7t), a2z,() to e,(dn), which implies a necessity for one or more

vacancies in the eg(dn) orbital of the metal and reduction potentials which are not too

negative.80,81

Finally, pseudonormal hyperporphyrins include VO(IV), Cr(II), Mn(II),

Mo(IV), La and Ac where S # 0. These metals show normal absorption spectra with a

weak extra absorption possible in the far-red region. All of these metals have a

partially filled or empty e,(dt) orbital, but charge-transfers from the porphyrin to the

metal are too high in energy to be observed in the UV-vis region. In addition, further

reduction takes these metals to unstable oxidation states which makes this an even

higher energy transition and highly unlikely 80,81









In addition to intramolecular effects such as the metal, substituents, and axial

ligands, intermolecular effects such as aggregation can significantly alter the electronic

behavior of porphyrins. Aggregation in these chromophores has been described

thoroughly by Kasha's exciton theory. This theory looks at aggregation only from the

point of view of overlapping transition dipole moments (Figure 1.15) and not as

interacting x-systems. In metallo-porphyrins, the transition dipole moments are

equivalent due to the symmetry of the chromophore.76,82,83


Figure 1.15: Transition dipole moments in metallo-porphyrin.


Aggregation, according to Kasha's model, splits the excitation energy of the

monomer (E) into high and low energy components. Equation 1.8 describes the

energy dependence on aggregation by:


Et =EO +DV


(1.8)


where D is the dispersion energy which is highly dependent on the change in

environment upon aggregation, and V is the exciton splitting energy. 76,83,84









When the chromophores are interacting with the transition dipole moments
parallel, the exciton energy can be described by Equation 1.9:



V -= M 1, (-cos a)) (1.9)



where M is the transition dipole moment, R is the center-to-center distance, N is the
number of chromophores, and a is the angle between R and M (Figure 1.16). So, if a
< 54.7, V will be positive, and the exciton splitting will be greater and a red shift will

be observed as the transition shifts to lower energy. A red shift is observed in what are
called J-aggregates where both M, and My make angles less than 54.7 with the R

vector. If a > 54.7, V will be negative, and the exciton splitting energy will be lower

leading to a blue shift in the spectrum. When M, and My are both greater than 54.7
from R, the aggregates are termed H-type. If ac < 54.7 and ay > 54.7 the spectral
components will split and part of the band will shift red and part will shift blue; this

spectral behavior is seen in edge-to-edge type aggregates. There can be combinations
and varying degrees of these types of interactions within an aggregated domain

possibly leading to complicated spectra, but in general, the optical spectra ease

identification of electronic behavior of porphyrin chromophores (Figure 1.16). 76,83,84













A.R.




A B C


Figure 1.16: Porphyrin chromophore interactions: The square represents the
chromophore and its disecting axes. A) H-type or face-to-face aggregates; B) edge-to-
edge aggregates; C) J-type or head-to-tail aggregates.

The transition dipoles Mx and My are typically parallel to the plane of the
chromophore except when the nature of the metal in the chromophore center causes a
puckering of the ring. Therefore, polarized UV-vis experiments can easily indicate
orientational changes of the chromophore within a film (Figure 1.16).76,83,84
Incorporation of porphyrins into LB films is currently of interest in scientific

literature. These films are designed in order to prepare selective gas-sensors,1,74,75
photovoltaic devices,85 electron-transfer materials,72,86 molecular wires,87 and novel

heterogeneous catalyst systems.88 However, a difficulty arises in the stability of the
samples using the "typical" LB methods of purely hydrophilic/hydrophobic
interactions or by self-assembly involving tethering through a ligand. Including a
metal-phosphonate lattice into these films should significantly improve the stability
and the applicability of these materials in ultra-thin, organized films.
Typically, LB films containing porphyrin constituents have been studied in
which the chromophore itself is the polar head group. These porphyrin films have
been successfully prepared with either the molecule sufficiently diluted with a film
stabilizing amphiphile,33,88-90 such as stearic acid, or with long hydrophobic chains









attached to the chromophore to stabilize the monolayer on the water surface.84,91

There are significant disadvantages to this method of film preparation. First, the

chromophore is buried in the film interior on a transfer onto a hydrophilic substrate,

and commonly, the hydrophobic interactions necessary to deposit onto a hydrophobic

substrate are too weak for successful transfer. Also, the hydrophilic interactions are

typically of a hydrogen-binding nature making this a relatively weak interaction

destabilizing the film. Finally, the conditions necessary for transferring the traditional

porphyrin LB films facilitate aggregate formation, which can be detrimental in certain
applications, such as catalysis.

The aggregation, or chromophore n-n interactions, is often a consequence of

the film forming procedures. First, compression of the film on the water surface

forces the eventual overlap or tilting of the chromophores.84,88,90 Also, the decreased

affinity of the derivatized chromophores for water tends to force the chromophores to

aggregate rather than to spread on the water surface.92 Understanding the molecular
orientation, aggregation, and morphology ofporphyrin LB films is critical because

each is intimately linked to chromophore behavior. For example, aggregation can

significantly reduce or eliminate the efficiency of the porphyrin in catalysis76 or the

ability of the porphyrin to bind probe molecules in a sensor.92 Therefore, it is

desirable to find methods for forming porphyrin LB films with no aggregation.


1.3.2. Background on Manganese Porphyrins

Biomimetic systems involving porphyrin catalysts have often been discussed in
scientific literature over the past 20 years. Manganese and iron porphyrins are

commonly studied oxidation catalysts and are prevalent elements in biological

processes.93-96 Biochemical oxidation reactions employing metallo-porphyrins

involve reversible site-specific binding of the substrate such that the substrate is within









reach of the oxygen atom on the metal. After the oxygen has been successfully

transferred to the substrate, the product is released and the catalyst is regenerated.93

Manganese porphyrins are probably most well known as epoxidation and

hydroxylation catalysts whether under heterogeneous or homogeneous conditions.

The manganese porphyrin catalysts can utilize a number of different oxidants such as

iodosylarenes, alkylhydroperoxides, hydrogen peroxides, and perchlorates among

others, in order to accomplish the facile oxidation of deactivated olefins, alkanes,

alcohols, ethers, and amines.97-100 A hyper-valent metal-oxo species is believed to be

the active intermediate in the oxidation process in cases such as dioxygen activation of

Cytochrome P-450, or in oxygen transfer from iodosylbenzene, peracids, or

hypochlorite oxidants.101 Though there is some debate on the actual mechanism of the

epoxidation, there are a few possible routes (Figure 1.17). The suggested first and

rate-determining step is the formation of a charge-transfer complex. Whether the

reaction then proceeds through epoxidation or rearrangement is dependent on the

oxidation potentials of the alkenes and the oxidants, steric and electronic structures of

the reactants, and the ability of the substrates to undergo rearrangement.97

Porphyrins have also been studied in chiral catalysis. Lai and co-workers studied

the asymmetric aziridation of alkenes using a chiral manganese porphyrin catalyst.102

They found that with bulky chiral substituents on the porphyrin, successful nitrene

transfer to alkenes was achieved. Enantiomeric excess ranging from 43 to 68% and

product yields greater than 70% were obtained. In these catalysis studies, the reactive

intermediate was a Mn(IV) complex.












oxidant



0

concerted /
oxene insertion .. -



I < / \



possible rate-limiting
formation of a charge-
transfer complex
Figure 1.17: Suggested mechanism ofolefi epoxidation catalyzed by MnTPP.


1.3.3. Immobilization of Porphyrins

The ability of porphyrins to efficiently catalyze both the epoxidation of olefins

and the hydroxylation of alkanes unfortunately leaves the porphyrin and its

superstructure vulnerable as potential substrates. However, nature has developed

mechanisms to eliminate these unwanted complications. For example, an enzyme and

its cofactors may form metal-oxo complexes only when the substrate molecule is

confined within an enzymatic cavity. Also, the tertiary protein structure prevents the
active porphyrin catalyst from approaching other potentially oxidizable
metalloporphyrins, and it makes the structure rigid, protecting the amino acid
backbone and the side-chains from intermolecular oxidation by contacting the active
site. These biosystems are difficult to mimic in the laboratory; however, successful









biomimetic catalysts have been prepared with bulky, rigid groups substituted on the

porphyrin chromophore.l10

One alternative solution to the problem of internal oxidation or intermolecular

oxidative destruction of the porphyrin catalyst is immobilization of the chromophore.

Immobilization involves tethering the porphyrin to a surface such as a film,88 an

inorganic solid particle,103-106 a polymer,107,108 a membrane,109 or a resin.110

Immobilized porphyrins as biomimetics and as heterogeneous catalysts have been well

explored in the past several years.104-106,110 Tethering of porphyrins to a solid support

can not only reduce or eliminate oxidative destruction of the active catalyst, but can

also aid in the catalyst recovery after the reaction is completed.

Heterocyclic ligands are commonly used as the link between the porphyrin and

surface in many immobilized porphyrin systems.94,98,111 Unfortunately, binding the

metallo-porphyrin to the imidazole allows little control over the porphyrin orientation

in the films. Additionally, in these circumstances, there is no chemical connection

between the porphyrin and the surface other than the ligand, which leaves the

porphyrin vulnerable to removal from the surface by ligand displacement, changing

the reaction conditions.30,94,98,'11 An alternative method for tethering the porphyrins

to surfaces has been established, which uses four alkyl phosphonic acid substituents

that can be attached to a zirconium phosphonate network making a very stable

catalytic film.


1.3.4 Heterocyclic Ligand Cocatalvsts

1.3.4.1. Ligand activation of the porphyrin catalyst. Heterocyclic ligands are
well documented in the literature as activating Fe(III) and Mn(III) porphyrins for

catalysis with oxidants such as alkyl or hydrogen peroxides.94,98,99 Porphyrins









immobilized on an ion-exchange resin support showed significant increases in

catalytic activity in the presence of either imidazole or 4-methylimidazole. With the

heterocyclic ligand present, nearly quantitative conversion of cyclooctene to

cyclooctene oxide was achieved, relative to only 5% conversion in the absence of

imidazole over the same time period.112 Likewise, Arasasingham et al. found a 4 to

10 fold increase in the rate of the reaction between a manganese porphyrin and an

oxygen source commonly used in olefin epoxidation reactions, t-BuOOH, in the

presence of imidazole. Since the oxidation of the porphyrin accelerates, a rate increase

should also be observed in the overall epoxidation reaction.98

According to Yuan and Bruice, the reaction of the Mn(III)TPP Cl complexes

with peroxide oxidants only proceeds in the presence of a heterocyclic nitrogen base

ligand such as imidazole or pyridine. The imidazole ligation was pH dependent and

was evident only above pH 5. Consequently, the enhanced oxidation rate was also pH

dependent. Further, with common oxidants, nitrogen base ligation led to a significant

increase in the oxygen transfer rate. 11

The rate increase could be due to a general-base catalysis and/or ligation of the

imidazole (ImH) to the manganese ion.98 Activation by ligation ofImH is supported

by the fact that when 2,4,6-trimethyl-pyridine is used as the base, which is sterically

forbidden from porphyrin ligation, no increase in the reaction rate was observed.

However, when the ImH concentration was below a saturation level, the rate increase

was linear with ImH concentration up to a saturation level. An increase in the

oxidation rate with a basic ligand is likely due to the increase in the electron density at

the metal center arising from donation of the lone pair of electrons from the ImH.98

The presence of the ImH as an axial ligand has been shown also to stabilize the metal-

oxo compound.99









1.3.4.2. Spectral evidence of axial ligand. ImH to porphyrin binding should be

apparent in the UV-vis spectra. The formation of a bis-imidazole Mn(III)TPP Cl

complex was demonstrated by a broadening shift in the Soret Band from 478 nm for

the pure porphyrin to 472 nm. ll Interestingly, the equilibrium constants for the

formation of the mono- and bis-ligated imidazole-porphyrin complexes are similar and

their absorption spectra are nearly identical. Therefore, at high concentrations of

imidazole in solution, it is possible that the observed spectra arise from the formation

of bis-imidazole complexes. 11,1 13 However, the preferred formation of the mono- vs.

bis-imidazole complexes has caused some disagreement, and some authors claim that

even at saturated concentrations of imidazole, the principal component is the mono-

imidazole only.114

In the UV-vis of the Mn-porphyrin, the Soret Band of the Mn-porphyrins is the

most sensitive to the axial ligand. The change in the Soret energy is due to the charge

induced on the porphyrin chromophore through the metal. Electron-donating axial

ligands induce negative charge on the macrocycle, separating the bonding and anti-

bonding orbitals of the porphyrin, and increasing the transition energy.115 Hard

anions, whose binding is strengthened by increased ionic character of the central

metal, prefer localization of positive charge on the metal, which leaves the

chromophore with more negative charge.15 Similarly, as a basic ligand takes on more

hard base character, the X, will shift to higher energies.


1.4 Dissertation Overview


The overall goal of this dissertation was to prepare zirconium phosphonate thin
films by both the SA and LB technique that contained catalytic Mn-porphyrins. The

purposes of the zirconium phosphonate network were to stablize the manganese









containing films to reaction conditions and to allow these films to be recycled in a

number of catalytic studies. Chapter 2 is an overview of the experimental techniques

used to prepare and characterize the films described in this dissertation, and materials

and instrumentation used in this pursuit are also presented.

Films containing a Pd-tetraphenyl porphyrin were prepared to develop film

preparation procedures and to better analyze the UV-vis properties of porphyrin

containing films. Substituted tetraphenyl porphyrins, palladium 5,10,15,20-

tetrakis(2,3,5,6-tetrafluorophenyl-4-octadecyloxyphosphonic acid)porphyrin (PdP4)

and palladium 5,10,15-tris(2,6-dichlorophenyl)-20- (2,3,5,6-tetrafluorophenyl-4-

octadecyloxyphosphonic acid)porphyrin (PdP ), have been studied as Langmuir

monolayers and as zirconium phosphonate LB and SA films.

Films were prepared incorporating the pure porphyrins and the porphyrins

mixed with octadecylphosphonic acid (ODPA). The Langmuir monolayers were

characterized with pressure vs. area isotherms and reflectance UV-vis spectroscopy.

Using a three-step deposition technique, symmetric and alternating zirconium

phosphonate bilayers and multilayers were prepared by the LB technique. PdP4

containing films were also prepared by the SA technique. In all PdPI and PdP4 films,

the porphyrin constituent resided in the hydrophobic region of the monolayer and the

phosphonate substituents bound zirconium ions in the hydrophilic region.

LB and SA films were studied with transmittance UV-vis and the LB films

were further investigated using X-ray diffraction. Control over chromophore

interaction was achieved by chemical modification of the amphiphiles and by selection

of appropriate transfer conditions. For example, reduced aggregation was seen in LB

films of the tetraphosphonic acid substituted porphyrin PdP4 transferred at mean

molecular areas (MMA) larger than the area per molecule of the substituted porphyrin

and in SA films. In these films, the porphyrin macrocycles are non-aggregated and









oriented parallel to the surface. In contrast, the monophosphonic acid substituted

PdPI aggregates under all of the deposition conditions studied.

Stability of the Pd-porphyrin LB and SA films was examined by exposing the
films to refluxing chloroform. UV-vis absorbance after immersion in chloroform

confirmed conclusions that in films of PdP 1, many of the chromophores are not

tethered to the inorganic network and are easily removed, whereas in films of PdP4, all

molecules bind to the zirconium phosphonate extended network making these films

very resilient.

Study of the Pd-porphyrins led to significant understanding of the behavior of
tetra- and mono-phosphonic acid porphyrins in LB films. Chapter 3 describes the

results of these studies, which were the first to show incorporation of porphyrins at the

exterior of metal-lattice containing films.

Manganese tetraphenyl porphyrins are well known epoxidation

catalysts,97,99,116 and the incorporation of these catalysts into zirconium phosphonate

films should improve their catalytic efficiency as well as their stability and

recoverability. Films containing manganese 5,10,15,20-tetrakis(2,3,5,6-

tetrafluorophenyl-4-octadecyloxyphosphonic acid)porphyrin (MnP4) have been

prepared using the LB and SA techniques. The formation of these films involved

modifying traditional LB procedures with SA techniques, which is possible with the

use of zirconium phosphonate networks. From Langmuir monolayer and LB studies

of the pure tetraphosphonic acid porphyrin, it appears that the MnP4 amphiphiles tend

to form face-to-face aggregates, or H-aggregates, when assembled at the air-water

interface, and this aggregation is translated into the transferred films. Attenuated total

reflectance (ATR) IR, UV-vis, XPS and stability studies confirm the presence of the

porphyrin. Thorough characterization of the MnP4 containing films is described in
Chapter 4.









The heterocyclic imidazole ligand has been shown to improve the catalytic

efficiency of Mn-porphyrins, and MnP4 films containing the imidazole ligand have

been successfully developed. These films were prepared by a variety of methods

involving a combination of LB, SA and substitution procedures. In solution, it is seen

that binding of a non-amphiphilic imidazole causes a small blue shift of the Mn-

porphyrin Soret band; however, a dominant influence on the Soret band in the films
and in solutions containing the ImODPA ligand comes from the metals axial

environment -- especially halide binding. Mixed films containing both the imidazole

phosphonic acid (ImODPA) and the MnP4 molecules have been prepared and

characterized by ATR-IR, UV-vis, and XPS. The preparation and characterization of

imidazole and MnP4 containing films is presented in Chapter 5.

The epoxidation of cyclooctene using iodosylbenzene was catalyzed by the

pure MnP4 containing films with substrate to oxidant ratios of 20:5, 40:5, and 60:5

over a variety of reaction times. The self-assembled MnP4 films proved to have

slightly improved catalytic efficiency relative to the analogous LB films likely due to

the increased aggregation observed in LB deposited films. The mixed

ImODPA/MnP4 films showed catalytic activity in the presence of the peroxide

oxidants. These films were examined with different substrate to oxidant ratios. The

porphyrin containing films, both with and without ImODPA were resistant to

degradation under most examined reaction conditions. The catalysis results involving

both PhlO and H202 oxidants with pure porphyrin and mixed porphyrin/imidazole

films are described in Chapter 6.









CHAPTER 2
EXPERIMENTAL



2.1 Langmuir-Blodgett and Self-Assembled Films



2.1.1. General Langmuir-Blodgett and Self-Assembly Procedures

2.1.1.1. Film Formation. The general procedure for forming LB films starts

with the Langmuir monolayer, which are prepared on a Langmuir trough. The trough

consists of a rectangular piece of Teflon, typically 1 cm deep, supported on a metal

base with Teflon barriers, shown as black rectangles in Figure 2.1. A Teflon well is

carved in the center of a double barrier trough for transferring monolayers. The

spreading solution is prepared by dissolving the amphiphile of interest in a volatile

solvent, such as CHC13. The solution is carefully applied to the subphase surface,

ideally spreading the molecules uniformly over the surface.




T Syringe

Wilhelmy
Balance
Barrier Surfactant
i Bmolecule
Aqueous
Subphase


Teflon Trough Wilhelmy
Plate

Figure 2.1: Schematic of Langmuir-Blodgett trough and monolayer.









The amphiphiles are shown in Figure 2.1 as gray circles, representing the

hydrophilic head group, and black lines, representing the hydrophobic tails. The

subphase, which is usually aqueous, must be nanopure. Because there is such a small

amount of amphiphile present, the monolayer is extremely sensitive to contaminants -

especially lipids and other surfactants and ions found in soaps and tap water.

The barriers compress the amphiphiles at a constant speed. In studying the H-

A isotherm, the film is compressed until it collapses. For LB transfers, the film is

compressed until the desired transfer pressure is achieved. At this point, the

monolayer is held at constant pressure for approximately two minutes until the

monolayer is stabilized, then the solid substrate is dipped vertically down through this

monolayer.

The monolayers are first characterized with II-A isotherms. In modem

computer operated systems, the concentration (mg mL"') and the molecular weight (g

mol-1), or the concentration in mol L', of the compound being spread is entered into

the program along with the spreading surface area in mm2. From this information, the

program can calculate the MMA in A2 molecule '. As the barriers move together and

the surface is compressed, the effective MMA is decreased and the surface pressure

increases.

The preparation of the zirconium phosphonate porphyrin films took place by a

three-step deposition procedure (Figure 2.2).28,29,38 A glass sample vial was placed in

the subphase in the well of the trough. Octadecylphosphonic acid was spread from 0.3

mg mL-1 CHC13 solutions and compressed at 15 20 mm min-1 on the water surface.

At 20 mN m-', the substrate was dipped down through the monolayer surface and into

the sample vial at 8 mm min-1, transferring the ODPA template layer. The substrate

and the vial were then removed from the trough and an amount ofzirconyl chloride

was added to the vial to make the solution ca. 4 x 10-5 M in Zr4+. After 20 min in the









zirconium solution, the substrate was removed from the vial and rinsed with water.

After the template layer was successfully prepared, it was dried and characterized

independently by ATR-IR, XPS, and UV-vis if needed.

Capping layers were prepared by a variety of methods, which will be described

for each different film type in Chapters 3, 4 and 5. LB or SA methods could be used

to form the capping layers. To form the capping layer and complete the zirconium

phosphonate bilayer by the LB technique, the now hydrophilic substrate was lowered

into the trough, a monolayer was spread on the surface and compressed to the desired

pressure, and the substrate was raised through the monolayer at 5 mm min7'. To form

the capping layer by self-assembly, the hydrophilic surface was submerged in a

solution of the desired molecules at about 10-5 M in an appropriate solvent, usually

EtOH/H20 (9/1). The capping layer was then allowed to self-assemble.

2.1.1.2. Materials and Methods. Materials used to prepare the porphyrin

containing films included octadecylphosphonic acid (ODPA), zirconyl chloride

(ZnOCI-8H20), and the porphyrins themselves. The porphyrins were provided by

Bruno Bujoli, Fabrice Odobel, Karine LeClair, and Laurent Camus from the

Laboratoire de Synthese Organique, at the Faculte des Sciences et des Techniques de

Nantes in Nantes, France. ODPA was used as purchased from Alfa Aesar (Ward Hill,

MA). Zirconyl chloride, 98% was used as supplied from Aldrich (Milwaukee, WI).

Octadecyltrichlorosilane (OTS) 95%, used to silanize and hence hydrophobicize the

substrates, was also used as purchased from Aldrich. Amylene stabilized HPLC grade

CHC13 was used as a spreading solvent, and was used as received from Acros

(Pittsburgh, PA) and Fisher Scientific (Pittsburgh, PA).

A KSV 2000 system (Stratford, CT) was used in combination with a

homemade, double barrier Teflon trough for the Langmuir monolayer studies and LB

film preparation.









STEP 1


1 01 Oi*


Transfer template
from water surface
STrnf tmle


' !i


SSample vial in trough


STEP 2


SA Porphyrin
(}^


V --*_-- *--1
I-- .--I

I |: I


Figure 2.2: Schematic of the three-step deposition process used for zirconium
phosphonate films.


STEP 3


Zr4+(


0 -









The surface area of the 2000 trough was 343 cm2 (36.5 cm x 9.4 cm). A

platinum or filter paper Wilhelmy plate, suspended from a KSV microbalance,

measured the surface pressure. Subphases were usually pure water with a resistivity of

17-18 MC cm-1 produced from a Barnstead NANOpure (Boston, MA) purification

system.

The films were transferred from the aqueous surface onto solid supports. Glass

microscope slides and glass coverslips were purchased from Fischer (Pittsburgh, PA)

and were used as substrates for UV-vis and catalysis studies. Single crystal silicon

wafers (1 00) were purchased from Semiconductor Processing Company (Boston,

MA), and cut using a diamond glass cutter to 25 mm x 15 mm x 0.8 mm for XPS

studies. These substrates were cleaned using piranha etch, which is 1:4 H2S04: 30%

H202, a new hydrophilic surface was prepared by the RCA procedure,117 which

involved first, heating in a 5:1:1 solution of water, 30% H202, and NH40H, and

second, heating in a 6:1:1 solution of water, 30% H202 and HC1. Then the substrates

were sonicated for 15 minutes each in methanol, 50/50 by volume methanol/

chloroform, and chloroform. The substrates were then sonicated in a 2%

octadecyltrichlorosilane (OTS) solution in hexadecane and CHC1, for two hours.

Finally, the substrates were sonicated for 15 minutes each in CHC13, 50/50 by volume

CH3OH/ CHC13, and CH3OH.118


2.1.2. Characterization

2.1.2.1. UV-vis. Transmittance UV-visible experiments were performed on a

Cary 50 spectrophotometer by Varian with an average resolution of 2 nm. Porphyrin

solutions were studied by UV-vis in EtOH, H20, CHC13, and CHCl2 solvents. The

behavior of the porphyrin with different potential ligands was investigated by mixing

the porphyrin solution with ethylphosphonic acid, t-butyl ammonium halides (chloride









and bromide) (Aldrich), and imidazole with no alkyl substituents (ImH) (Kodak). A 1

cm x 1 cm x 3 cm quartz cuvette held the sample, and the background using the

corresponding pure solvent was subtracted.

A Teflon substrate holder with grooves cut at 450 to one another was used to
obtain sampling at 0 (beam normal to the substrate) and 45* incidence to the substrate

surface. A plane, visible polarizer was used to select s- and p-polarized light.

Reflectance UV-vis experiments were performed on a KSV 2000 mini-trough using an

Oriel spectrophotometer and a 77410 filter with a range from 200 600 nm.

2.1.2.2. X-ray Photoelectron Spectroscopy. X-ray photoelectron spectroscopy
(XPS) was performed on a Perkin-Elmer PHI 5000 Series spectrometer using the Mg

Ka line source at 1253.6 eV. The instrumental resolution was 2.0 eV, with anode

voltage and power settings of 15 kV and 300 W, respectively. The operating pressure

was around 5 x 10-9 atm. Survey scans were performed at a 450 takeoff angle with a

pass energy of 89.45 eV. During multiplex scans, 80 100 scans were run at each

peak over a 20-40 eV range with a pass energy of 37.35 eV.

2.1.2.3 X-ray Diffraction. In order to obtain low angle X-ray diffraction
(XRD) patterns, multilayer films were transferred onto a hydrophobic glass slide. The

diffraction patterns were obtained using a Phillips APD 3720 X-ray powder

diffractometer with the CuKa line, X = 1.54 A, as the source for films ranging from 10

to 15 bilayers.

2.1.2.4. Attenuated Total Reflectance Infrared. Attenuated total reflectance

infrared spectroscopy was performed on a Mattson Instruments (Madison, WI)
Research Series-1 FTIR spectrometer equipped with a deuterated triglyceride sulfide

detector and a Harrick (Ossining, NY) TMP stage which held the Ge crystal substrate.

ATR-FTIR spectra consisted of 500 scans at 2 cm-1 resolution and were referenced to
the silanized crystal or previous bilayers.











2.2 Porphyrin Films


2.2.1. Palladium Porphvrin Films

The palladium porphyrins studied were palladium 5,10,15,20-tetrakis(2,3,5,6-

tetrafluorophenyl-4-octadecyloxyphosphonic acid)porphyrin (PdP4) and palladium

5,10,15-tris(2,6-dichlorophenyl)-20- (2,3,5,6-tetrafluorophenyl-4-

octadecyloxyphosphonic acid)porphyrin (PdPI). The Bujoli group provided us with

these porphyrin amphiphiles.

The Pd-porphyrins made well-behaved monolayers; therefore, these

amphiphiles were often transferred by the LB technique. Additionally, the Pd-

porphyrins were studied in diluted mixtures with ODPA in an attempt to disrupt the

aggregate formation in the films. For mixed, Pd-porphyrin/ODPA films, the two

materials were simultaneously dissolved in a CHC13 solution. The weighted average

concentration and molecular weight were calculated and used in the KSV software to

monitor the MMA with compression. Ratios of PdP (1 and 4) to ODPA studied

included 1:0, 1:1, 1:4, 1:9 and 0:1, respectively.

The creep of the pure palladium-porphyrin Langmuir monolayers was studied

at high and low pressures over 30 min, or slightly longer than the time of one

deposition. At a constant pressure of 12 15 mN m-1, the area changed by 6% and

12% for PdP4 and PdPI, respectively. At low pressure (3 5 mN m-1), the change in

area was 3% and 7% for PdP4 and PdP1, respectively. The instability in the

monolayers led to a necessary correction in the transfer ratios. The corrected transfer

ratios for the pure PdP4 were 1.0 1.4 at high pressures and 1.0 1.1 at low pressures.

For the pure PdPl, the corrected transfer ratios were 0.8 1.0 and 0.9 1.0 for high









pressure and low pressure transfers, respectively. The transfer ratios of the porphyrin

films mixed with ODPA consistently showed uncorrected transfer ratios near unity.

Monolayers of PdP1 and PdP4 were also studied on both heated and basic

subphases. To heat the trough, an Isotemp Refrigerating Circulating Model 900

(Fisher Scientific) pump with a water/ethylene glycol bath was used. The temperature

of the subphase was monitored using a KSV thermosensor. A 0.01 M KOH solution

was added to the subphase to adjust the pH to the desired value.

PdP4 films were also studied by self-assembly. The SA solution was prepared

by diluting 1 mL of a 0.5 mg mL"' solution of PdP4 in CHC13 to 30 mL with a 9/1

EtOH/H20 mixture. The film was allowed to SA for approximately 2 hours before

studying by UV-vis.


2.2.2. Manganese Porphyrin Films

Manganese 5,10,15,20-tetrakis(2,3,5,6-tetrafluorophenyl-4-

octadecyloxyphosphonic acid)porphyrin (MnP4) and a model porphyrin, manganese

5,10,15,20-tetrakis (pentafluorophenyl)porphyrin (MnPO) were prepared by the Bujoli

group. Again, ODPA was used for the template layers, zirconyl chloride was used to

prepare the zirconium network, and CHC13 was used as the spreading solvent. Also, t-

butylammonium chloride (t-BuNH2, CI) (Aldrich) was used as a chloride source for

SA deposited films. NaCI (Acros) was used as the chloride source for LB transferred

films.

To form the MnP4 monolayers, a 0.4 mg mL'1 solution was prepared in CHC13

(often, in order to dissolve the porphyrins, up to 5% ethanol was added and the

solution was sonicated for about an hour). An appropriate volume of solution was

spread on the aqueous surface in order to reach and hold the desired transfer pressure









throughout the deposition. A variety of surface pressures were used for transfer and

will be described in more detail in Chapter 4.

To prepare SA Mn-porphyrin films, 1 mL of a 0.5 mg mL"' MnP4 solution in

EtOH was diluted to 30 mL with a 9/1 EtOH/H20 mixture in a 50 mL vial.

Alternatively, a 0.5 mg mL'" MnP4 solution in CHCIl was diluted with pure CHCl1 or

CH2Cl2. The zirconated ODPA surface was exposed to the SA solution for 2 hr unless

otherwise specified. After 2 hr, there were typically some physisorbed chromophores,

which were rinsed off the surface using a hot solvent such as CHCl3 or CH3CN.

As is discussed in Chapter 4, halogenated solvents were originally chosen as

self-assembly solvents to eliminate possible ethoxide or water binding. However, the

oxide coating on the exposed zirconated ODPA template is soluble in EtOI/H20

solvents making the zirconium available for binding the phosphonic acids of the

porphyrin capping layer. From UV-vis studies, the films formed from these different

solvent systems appeared to behave similarly. Therefore, because the film formation

mechanism from EtOH/H20 was better understood, this solvent mixture was normally

used.

To induce chloride binding at the Mn-porphyrin's axial position, a SA solution

containing approximately 0.01 0.1 M t-BuNH3I ClI along with the porphyrin in

EtOH/H2O was prepared. The zirconated ODPA template was submerged in this

solution for 2 hr. Alternatively, chloride ions were incorporated into the aqueous

subphase used for LB transfer of the MnP4 monolayers using NaCI at 0.1 M and

greater concentrations.

From UV-vis results of the MnP4 and MnPO with ethylphosphonic acid, it

appeared that the phosphonic acid might cause the Mn(III)-porphyrin to go through a

spin state crossover from high-spin to low-spin Mn(III). In order to examine this

magnetic change, the Evan's NMR method was used.119,120 A solution of 10% t-









butanol in CDCl3 was injected into a small capillary tube using a long syringe needle.
The depth of the solution in the capillary tube reached approximately 2". Two
standard NMR tubes were then filled to approximately 1" with sample solution. The
first was filled with pure MnPO (0.0106 g, 100 pmol) dissolved in the 10% t-

butanol/CDCl3 solution. The second was filled with MnPO (0.0106 g, 100 pmol) and

ethylphosphonic acid (0.220 g, 2000 pmol). The reference solution in the capillary
was inserted into the porphyrin containing NMR sample, and the magnetic

susceptibility of the solute, Xg (cm3 g'-) induced by the magnetic porphyrin was

approximated by:



-3Af
f (2.1)



where Af is the diamagnetic frequency shift, f is the spectrometer frequency, and m is

the mass of substance per mL of solution. Compared to literature values, the
differences in the X8 of MnPO with and without ethylphosphonic acid did not
correspond to a spin state change in the Mn(III).


2.2.3. Manganese Porphyrin/Imidazole Mixed Films

The general method used to prepare MnP4/imidazole films in this study
involved the initial formation of a zirconated octadecylphosphonic acid (ODPA)

template, as before. Onto this template, a film of either pure imidazole
octadecylphosphonic acid (ImODPA), which was prepared by the Bujoli group, or a
mixture of ImODPA and MnP4 could be formed. The zirconium phosphonate
network provided a means for locking the porphyrin and the imidazole into the films,
resulting in films that were stable toward the conditions used for the catalysis









reactions. Even under relatively harsh conditions such as elevated temperatures or

rapid solvent flow, the porphyrins films appeared to be stable. Additionally, the

zirconium phosphonate network made preparation of the MnP4-imidazole films

possible by a wide variety of mechanisms.

MnP4 and ImODPA could be incorporated into both LB and SA films. In
order to accommodate ImODPA into LB films, two types of spreading solutions were

used: 1) ImODPA mixed with a stabilizing agent such as hexadecylphosphonic acid
(HDPA), or 2) ImODPA mixed with the MnP4 amphiphile. Alone, the ImODPA did

not form sufficiently stable monolayers for transfer. The porphyrin, MnP4 was

substituted into the films of pure ImODPA or ImODPA/HDPA from an EtOH/H20

solution. Alternatively, the MnP4 film was transferred by the LB technique and then

the ImODPA was substituted into these films.

First, in the case of the mixed 25% ImODPA/75% HDPA films, 200 gL of a
solution with a weighted average concentration of 0.17 mg/mL and a weighted average

molecular weight of 329.86 mg mmol"' was spread on the water surface and

compressed to 12 mN m-'. The film was transferred at 5 mm min' on the upstroke

completing the zirconium network. Films made in this way were abbreviated

ODPA/Zr/25% ImODPA. These films were then placed in a solution of the MnP4 at

ca.10-5 M in 9/1 EtOH/H20 and the porphyrin phosphonic acids were allowed to

substitute into the defect or vacant sites in the film for 2 hr. Transmission UV-vis of

these films confirms the ability to include the porphyrins by this method, and the

resulting films were called ODPA/Zr/25% ImODPA, SA MnP4.

Films containing both the MnP4 and the ImODPA transferred by the LB
technique from a mixed monolayer were also prepared. A 70/30 mixture of
MnP4/ImODPA, respectively, was dissolved in CHC13 with a weighted concentration

and MW of 0.289 mg/mL and 992.70, respectively. 175 pL of this solution was









spread and transferred at 3 mm min"' on the upstroke forming the ODPA/Zr/30:70

MnP4:ImODPA films.

For the self-assembly of the imidazole onto a zirconated ODPA template, 2 mL
of a 0.5 mg mL-' solution of ImODPA in EtOH was dissolved in a 9/1 EtOH/H20

mixture in a 50 mL vial. The substrate containing the zirconated ODPA template was

placed in the vial and the film was allowed to self-assemble for 2 hr. When the self-

assembly procedure was complete, the film was rinsed with nanopure water and dried

with forced air. The MnP4 molecules were allowed to substitute into these films as

described in section 2.3.2. Similarly, mixed MnP4 and ImODPA solutions were

prepared at a variety of ratios in EtOH/H20, and the mixed monolayer was allowed to

self-assemble for 2 hr.

The ImODPA was deprotonated as mentioned in Chapter 5 by soaking the
mixed film in an EtOH solution containing t-butyl amine. The t-butyl amine was used

to deprotonate the imidazole within the films so the ligand would be available for

binding the central manganese. The concentration of this solution was not precise but

was consistently ca. 0.1 M and rinsing times were ca. 15 min.


2.3 Catalysis


2.3.1. Catalysis using PhIO as an oxidant

Pure porphyrin films behaved as catalysts for the epoxidation of cyclooctene
using iodosylbenzene (PhIO) as the oxidant. PhIO was synthesized from the diacetate

precursor using NaOH.121 Iodobenzene diacetate (3.0 g, 9.3 mmol) was placed in an

Erlenmeyer flask. 30 mL of 3 N NaOH was added with stirring over 5 min. The

mixture was stirred for 15 min and left to sit uncovered 45 min. 100 mL deionized

H20 was added with stirring and the yellow solid was filtered using a Buchner funnel.









The solid was collected and washed with another 100 mL aliquot of H20. The solid

was filtered again, and washed with CHC13 2 times in a beaker and filtered. The solid

was dried in a vacuum desiccator. The product's melting point corresponded well to

the literature value of 210 C. Iodometric titration, involving converting the PhIO

product to Phi and I2 with HI and titrating with sodium thiosulfate, gave a purity of
99%.122

PhIO (27.5 mg, 125 pmol) was diluted in 25 mL CH2Cl2. The PhIO compound
was only slightly soluble in CH2C12, so it was diluted and then sonicated for at least 30

min. After sonicating, an amount of the cyclooctene was added and the mixture was

stirred for about 1 min. Decane (97 gtL, 500 imol or 24 jL, 125 Pmol), the internal

standard, was also added with stirring. ImL samples of this mixture were used for

both a blank run and a homogeneous run. In all homogeneous experiments, 1 jL of a

1 mM solution of MnPO was added to the blank solution to investigate the epoxide

yields with the porphyrin in solution.


Outlet port Inlet port


I L



Screws to hold
Su cells together


Figure 2.3: Schematic of catalysis cell, side view.






55


Approximately 5 mL of the above oxidant/substrate solution was transferred
into a small Erlenmeyer flask and from there loaded into the flow cells used for

studying catalysis with the films. Also, blanks and homogeneous solutions were

loaded into cells containing blank films (no catalyst) for studying product yields

affected by the flow cell.


Groove with
Viton cell: roove with Viton cell:
Bottom plate Von Top plate




0.06" wide
ledge



Inlet/Outlet ,
hole

Figure 2.4: Schematic of catalysis cell, top view.


The flow cells were built by the University of Florida machine shop. The cell
was made from two blocks of Delrin into which was carved a cell with dimensions:

0.96" x 1.38" x 0.039". Inlet and outlet tubes were place at the cell edges. One end

of a 1' length of 1/16" ID Viton tubing (Cole-Parmer, Vernon Hills, IL) was

connected to the inlet port and the other end was submerged in the reaction solution.

A Cole-Parmer Masterflex peristaltic pump (model 7553-70) (6-600 rpm) with an
easy-load head was used to introduce the solution into the cell, then the open end of

the Viton tubing was removed from the solution and connected to the outlet port of the

cell. The solution was circulated around the film using the peristaltic pump.









The reaction products were studied by GC. The GC instrument was a
Shimadzu GC-17A (Columbia, MD) with a hydrogen flame ionization detector. A 1

p.L portion of the reaction solution was injected onto the 25 m, 0.025 mm ID RTX-5

column (Crossbond, 5% diphenyl-95% dimethyl polysiloxane). The column was held

at 500 C for 3 min and then ramped at 100 C minm' for 15 min.

Sensitivity factors (k) were determined using decane and o-dichlorobenzene as
the internal standards. A series of runs were performed for both the cyclooctene

(CyO) and the cyclooctene oxide (CyOO) standards. Equation 2.2 was used to
calculate 'k' from the GC trace areas of the standard (AJ and the product (Ao) and

the known sample weights (wcoo and w,).




kco = WcO(2.2)



After an average k value was obtained for the CyO and CyOO, the catalysis yields

were determined from the reaction mixture using Equation 2.3:




WCyOO = ----koosA (2.3)



Because the PhIO oxidant was rather insoluble, a series of 1 mL aliquots of a
1.1 g L'' solution of PhIO in CH2C12 were dried and weighed. The final weights were

1.1 mg 9%, assuring us that the amount of oxidant in each reaction was

approximately the same.

In order to compare nearly the same concentrations of catalyst in both the
homogeneous and heterogeneous cases, the concentration ofporphyrins in the films









was calculated to be, at most, 1 nmol. In was, however, difficult to keep this

concentration constant. In the homogeneous reactions, 1 nmol of the corresponding

non-amphiphilic MnPO was used.

Imidazole is reported to improve the catalytic efficiency of the Mn-porphyrins

in the presence of a peroxide oxidant, but for comparison, we also tried to see if

imidazole would improve the catalytic efficiency in the presence of PhIO. For this

experiment, 0.1 tmol of ImH was added to the blank and homogeneous solutions

using a PhIO solution with 40 pmol CO, 5 pmol PhIO and 20 umol decane. Also,

films prepared by SA ImODPA and SA MnP4 were used in the flow cells with this

same PhIO solution. The reactions were, again, stirred for 24 hr.


2.3.2 Catalysis using peroxide oxidants

In studying the catalysis of the epoxidation of cyclooctene (CyO) with H202,

many different substrate to oxidant ratios were studied. The epoxide yields were

greatest, however, when very dilute solutions of reactants were used to keep the

proportion of reactants to catalyst near a factor of 10 and the substrate was used in

excess. The starting materials, CyO and H202, were dissolved in 250 mL of CH2C12

with o-dichlorobenzene as the internal standard. ImL aliquots of this solution were

used for the reaction blank and homogeneous reactions and contained 8 umol CyO,

0.2 pLmol H202, and 0.2 p.mol of o-dichlorobenzene. To the homogeneous reaction

were added 0.4 imol ImH and 0.001 upmol of MnPO. The original solution was

pumped into the flow cells using the peristaltic pump, and these reactions were

allowed to stir for 24 hr at room temperature.













CHAPTER 3
PALLADIUM PORPHYRIN CONTAINING ZIRCONIUM PHOSPHONATE
LANGMUIR-BLODGETT FILMS


3.1. Background on Palladium Porphyrin Films


Langmuir monolayers and LB films of the derivatized palladium tetraphenyl

porphyrin molecules, palladium 5,10,15,20-tetrakis(2,3,5,6-tetrafluorophenyl-4-

octadecyloxyphosphonic acid)porphyrin and palladium 5,10,15-tris(2,6-

dichlorophenyl)-20- (2,3,5,6-tetrafluorophenyl-4-octadecyloxyphosphonic

acid)porphyrin, referred to as PdP4 and PdP1, respectively, are described in this

chapter. The central Pd metal is a four-coordinate, diamagnetic ds metal, and is co-

planar with the porphyrin ligand. Being four-coordinate, there are no complicating

axial ligands to consider.

Porphyrins PdP4 and PdPI are substituted with four and one

octadecylphosphonic acid groups, respectively. These molecules differ from many

other porphyrin amphiphiles in that there is a hydrophilic group at the end of the alkyl

chain substituent. In many literature reports, the porphyrin group is often the

hydrophilic part of LB film forming amphiphiles.91 Molecules PdP4 and PdPI

(Figure 3.1) were designed to investigate whether porphyrins can be incorporated into

metal phosphonate LB films. Also, because of their well-understood spectroscopic

behavior, the PdP molecules were used to study how the orientation and aggregation

of the porphyrin can be controlled in the deposited films.











8P03H2 (R)


R O(CH2)18P03H2


A B
Figure 3.1: Structures of A) PdP4 and B) PdP1.


Palladium polyhalogenated porphyrins were chosen based on the following
considerations. First, palladium porphyrins are not demetallated in acidic conditions,

and their diamagnetic character makes following the synthesis with NMR

spectroscopy possible. Second, manganese and iron polyhalogenated porphyrins are

well-known catalysts for the oxidation of hydrocarbons;123 therefore, if palladium is

replaced by one of these metals, the films can be used for catalytic applications.

Third, pentafluorophenyl substituents on porphyrins allow straightforward

functionalization of this ligand by aromatic nucleophilic displacement with an alcohol.
In addition, the ether bonds are more stable toward hydrolysis and less hydrophilic
than the ester or amide linkages usually used to tether alkyl chains on porphyrins.

High hydrophobicity of the linkage is a requirement because competition with the

polar phosphonic acid head-group should be avoided during the LB film preparation.








LB films of PdP4 and PdPI were formed incorporating a zirconium
phosphonate network. The strong tendency of zirconium ions to crosslink the
phosphonate groups precludes the normal deposition of organophosphonate

monolayers with the metal in the subphase.28 Therefore, a previously developed

three-step deposition procedure was used (Figure 2.2) as described in Chapter 2.28,38
Both symmetric (PdP/Zr/PdP) and alternating (ODPA/Zr/PdP) films have been
prepared in this way (Figure 3.2).



a b c d





Zr Zr Zr 'Zr






Hydrophobic Substrate

= PdP1 and PdP4 = OPA





Figure 3.2: Schematic of Pd-porphyrin films formed: a) alternating ODPA/Zr/PdP, b)
alternating ODPA/Zr/PdP:ODPA mixed film, c) symmetric PdP/Zr/PdP, d) symmetric
PdP:ODPA/Zr/PdP:ODPA.

Control over aggregation of the porphyrin chromophores is achieved through a
combination of molecular design and the careful choice of the conditions for transfer









of the films. Aggregation is decreased or eliminated in the films of the tetra-

substituted PdP4 when transferred at very high mean molecular area MMA and at high

subphase pH. Mixtures of this amphiphile with ODPA transferred at high

temperatures (400C) and high MMA showed a similar decrease in inter-chromophore

interaction. The four long-chain phosphonic acid substituents significantly aid the

spreading of monomeric porphyrin species and the strength of the zirconium

phosphonate interaction assures their isolation in the transferred films. In similar

studies of the mono-substituted PdP 1, aggregation was observed under all of the

transfer conditions explored, indicating that none of the deposition procedures

overcome the tendency of the molecules to aggregate.


3.2. Results


3.2.1. UV-vis of Palladium Porphvrin Solutions

The palladium porphyrins show spectral responses in the UV-vis consistent

with hypso-type metallo-porphyrins. For each porphyrin, a strong Soret Band (or B

Band) is present above 400 nm and two Q Bands are centered around 550 nm.80,124

Solution studies of the porphyrins PdP4 and PdP1 were performed in ethanol and

chloroform, and the absorbance dependence on concentration was investigated.

Solutions ranging from 10-11 M to 10-6 M were studied (Figure 3.3). In CHC13, the

Soret Band was consistently at 410 to 411 nm for the porphyrin PdP4. In CHC13,

therefore, PdP4 shows no sign of solution aggregation. For porphyrin PdP1 at 10-11

M, the Soret Band absorbed at 411 nm; however, as the concentration was raised, the

Band shifted to 414 nm. Because PdPI has only one long chain substituent, the

likelihood of aggregation is increased; therefore, in CHCl3, the PdP1 chromophores J-

aggregate at high concentrations.76,92 Interestingly, the Soret Bands for both PdP4










and PdPI absorb at 411 nm at 10-11 M, so the long chains have no effect on the Soret

Band of the non-aggregated chromophore.


0.10-


0.05-


0.00-

0.15-


0.10-


0.05-


0.00-


Wavelength (nm)


Figure 3.3: Solution UV-vis of Pd-porphyrins in CHCl3: A) PdP4, B) PdPl. The
absorbance scale refers to the 106 M curve. The 10"" M curve has been enlarged for
Band comparison.


The studies of the same molecules at identical concentrations in EtOH and

water showed very different behavior (Figure 3.4). In EtOH at 10-11 M, both PdP4 and

PdP1 show Soret Bands at 414 415 nm. This peak is significantly to the red of the

Soret Bands in CHCI3; however, it is known that more polar solvents tend to stabilize









the excited states in n-nt* transitions, shifting this Band to lower energies.25,26 As the

concentrations of both PdP4 and PdPI were raised, the Soret Band systematically

shifted blue to 407 and 411 nm for the porphyrins PdP4 and PdP1, respectively,

implying H-aggregation of the chromophores in EtOH.76,92 Going from EtOH to

CHC13 to H20, at 106 M, there is an obvious red shift in the X,. This red shift does

not correspond to a solvent polarity shift, but it does correspond to a shift in the

solubility of PdP4. PdP4 is very soluble in EtOH and only slightly soluble in water.


0.10

0.08

0.06

0.04

0.02

0.00


Wavelength (nm)


Figure 3.4 Solution UV-vis of PdP4 in EtOH and water compared to CHC13.



3.2.2 Langmuir Monolavers of Palladium Porphyrins

The room temperature pressure (H) vs. area (MMA) isotherm of PdP4 on water

at pH 5.5 is shown in Figure 3.5. There is a measurable onset of surface pressure near

220 A2 molecule-1, followed by a gradual increase in pressure as the film is

compressed, with an apparent phase transition giving a steeper rise in pressure near









115 A2 molecule-'. The MMA of the tetraphenyl porphyrin is 200 A2 molecule-'

implying that at the onset, the tetrasubstituted porphyrin molecules are not aggregated

or stacked.91 However, this arrangement is not stable to pressure, and as the film is

compressed, the molecules are forced to rearrange.


50 100 150 200
Mean molecular area (A2 molecule1)


Figure 3.5: Isotherms of PdP4, pure and mixed with ODPA (PdP4:ODPA), on a water
subphase.

The change in the aggregation of PdP4 during compression can be observed

with reflectance UV-vis spectroscopy of the Langmuir monolayer (Figure 3.6). As the

film is compressed from a MMA of 370 A2 molecule-' through 220 A2 molecule-', the

Xmax remains between 416 and 417 nm, similar to the ,max observed for the non-

aggregated porphyrin in EtOH. At areas between 220 and 100 A2 molecule-', the Soret

Band shifts to 418 419 nm, and below 100 A2 molecule-' the Soret Band shifts

further to near 421 nm. The shift in the Soret Band suggests a change in the









interaction of the chromophores at different pressures. At MMA larger than and

comparable to the size of the chromophore itself, the porphyrin rings cannot be

aggregating to any significant extent or the onset of surface pressure would occur at

lower areas. The red shift of the Soret Band as the area is decreased indicates

enhanced chromophore aggregation at lower MMA.




0.10-

45 d d
00 I
0.08




0.04 0 (A1re1 nale") I

0.02 a

0.00

360 380 400 420 440
Wavelength (nm)




Figure 3.6: Reflectance UV-vis of PdP4 on water subphase.



In contrast to PdP4, the H-A isotherm ofPdPI (Figure 3.7) indicates that these

molecules aggregate even in the absence of applied pressure. No significant increase

in surface pressure is seen until areas below 120 A2 molecule-1. The pressure rises to

only 5 mN m-i at 60 A2 molecule-1, below which the pressure increases until the film

collapses below 36 A2 molecule-1. The isotherm cannot reflect a true molecular

monolayer, but rather results from the compression of aggregates at the water surface.









Evidence of aggregation at all MMA is seen in the reflectance UV-vis spectra. Figure

3.8 shows the Soret Band as a function of MMA from greater than 120 A2 molecule-'

to film collapse at 36 A2 molecule-1. The Soret Band does not shift during

compression, and the nmax of 426 nm indicates that the porphyrins are aggregated at

each stage of the isotherm.


Mean molecular area (A2 molecule1)


Figure 3.7: Isotherms ofPdPI, pure and mixed with ODPA (PdP :ODPA), on a water
subphase.

A common procedure for enhancing the stability and processibility of unstable

Langmuir monolayers, and to reduce aggregation, is to mix the amphiphile of interest

with a good film-forming amphiphile.33,88-90 In this pursuit, both of the porphyrins

were mixed with ODPA, which is a well-studied amphiphile that forms a liquid-

condensed phase on the water surface and easily binds to an exposed Zr-phosphonate

surface. As the percentage of ODPA is increased, the isotherms increasingly take on









characteristics of the liquid-condensed phase of ODPA, although features present in

the isotherms of the pure porphyrins are also present in the isotherms of the mixed

films (Figure 3.5 and 3.7).





0.12 -
50 .-'
0.10 -_40 f
E: 30
0.08 20 e
8 I1 C d
U 0.06- 0
f' 25 50 75 100125150
M MA (A' molecule')
00 b
0.02- a -

0.00

-0.02
360 380 400 420 440
Wavelength (nm)



Figure 3.8: Reflectance UV-vis of PdP1 on water subphase.



In addition, the collapse pressure increases with the concentration of ODPA indicating

that the films become more stable as ODPA is added. However, diluting the porphyrin

film with ODPA does not appear to greatly affect the aggregation. Reflectance UV-

vis of a Langmuir monolayer of a 1:9 mixture of PdP4 with ODPA is shown in Figure

3.9. The Xmax shifts from 415.5 nm at high MMA to 420 nm as the film is

compressed, just as it does in the films of pure PdP4 (Figure 3.9). However, the

porphyrins do not appear to be aggregated in the mixed film at high MMA.












0.03- 60 e e

45
d

C

0.01 2 30 40 50 b
I a
oMoW (A9 rr2eaie)


0.00


-0.01I
360 380 400 420 440
Wavelength (nm)



Figure 3.9: Reflectance UV-vis of 10% PdP4: 90% ODPA on a water subphase.



The molecular areas in Figures 3.5 and 3.7 are weighted averages of the

porphyrin and ODPA molecules. The MMA of the porphyrin molecules in the mixed

films can be calculated using Equation 3.1: 89



S (SPOR + NSOPA) (3.1)
(N+1)



where Smix is the MMA of the mixture determined from the isotherm, SPOR is the

MMA of the porphyrin within the mixed films, SODPA is the MMA of the ODPA

amphiphile in pure ODPA films, and N is the molar ratio of ODPA to porphyrin.

SPOR was calculated in the ODPA mixtures of each porphyrin at pressures of 5 mN m-1

and 15 mN m-1 and the results are plotted in Figure 3.10.






69







300
A 5 mN m1 75 B m 5mN m"
225- 15mN m-1 '-~ 15mN m

150- -

75. 25

01 0
0 2 4 6 81 10 0 2 46 81 0
N (OPA/POR) N (OPA/POR)



Figure 3.10: Mean molecular area vs. ratio of ODPA/Porphyrin: A) PdP4, B) PdPl.



If the ODPA diluent were breaking apart the preferred organization of the

porphyrins in the films, SPOR would increase as the aggregates separate. The decrease

in SPOR in the mixed films suggests that either the porphyrin chromophores are

reorienting in the mixed films or aggregation actually increases in the mixed films.

However, it does not appear that porphyrin aggregation decreases in the mixed

monolayers.



3.2.3 Langmuir-Blodgett Films

LB films of PdP4 and PdPI were prepared using the deposition procedure

described in Figure 2.2. The stepwise deposition allows fabrication of both symmetric

films, where the template and capping monolayers are the same, and alternating films,

where the two monolayers in the bilayer are different. Both types of films were

prepared for each porphyrin (Figure 3.2). It has been shown that a zirconated ODPA

template layer frequently provides the best substrate for transferring a capping layer.65


1









The extremely well organized and oxophilic surface allows deposition of almost any

phosphonic acid monolayer, including those that are not stable monolayers and would

normally not transfer. Monolayers of PdP4 and PdPI were transferred at a range of

temperatures, pressures and subphase pHs (Tables 1 and 2). Films of the porphyrins

mixed with ODPA were also transferred under a variety of conditions. Under some

conditions, perfect, organized monolayers were obviously not formed, but the films

could be transferred onto solid supports and studied.

3.2.3.1 Films of compound PdP4. To form alternating films of PdP4, the

Langmuir monolayers were transferred as capping layers onto zirconated ODPA

template layers. Films were transferred at different surface pressures and the Soret

Band of the transferred films was used to monitor differences in chromophore

aggregation in the deposited films. The UV-vis spectrum of a film transferred at 130

A2 molecule-1 (15 mN m-1) is shown in Figure 3.11, where the kmax of the Soret Band

appears at 420 nm, significantly red-shifted from any of the solution spectra of PdP4.

The red-shift suggests increased aggregation, which is expected because at such a

small MMA, the chromophores must be either tilting perpendicular to the surface and

organizing side-by-side, or sliding over one another to form bilayers or multilayers.

Polarized UV-vis spectroscopy indicates the porphyrins are oriented parallel to the

surface, implying the latter arrangement.

Layers of PdP4 were also transferred at 190 (12mN m-1) and

300 A2 molecule-' (Figure 3.11). The Soret Band shifts to 418 nm for the film

transferred at 190 A2 molecule-1 and to 416 nm for the film transferred at 300 A2

molecule-', indicating less aggregation in films transferred at high MMA. At these

larger MMA, the porphyrin chromophores should be lying flat at the air-water

interface with little aggregation and they appear to remain non-interacting when

transferred.









Table 3.1: UV-vis data from symmetric and alternating films of PdP4. L, is given
for monolayers, and interlayer thickness is given for multilayers of films transferred
under a variety of transfer conditions.

Film Transfer FI of pH*** Temp ,, thickness
Area Transfer (C) (nm) (A)
(A2 mol.')* (mN/m)


OPA/Zr/PdP4
OPA/Zr/ PdP4
OPA/Zr/ PdP4
OPA/Zr/ PdP4
OPA/Zr/ PdP4
OPA/Zr/ PdP4
OPA/Zr/10% PdP4
OPA/Zr/10% PdP4
OPA/Zr/25% PdP4
OPA/Zr/50% PdP4
OPA/Zr/ PdP4
OPA/Zr/ PdP4
OPA/Zr/ PdP4
OPA/Zr/ PdP4
OPA/Zr/ PdP4
OPA/Zr/25% PdP4
OPA/Zr/25% PdP4
OPA/Zr/10% PdP4
OPA/Zr/10% PdP4
PdP4/Zr/ PdP4
PdP4/Zr/ PdP4
10% PdP4/Zr/ 10%
PdP4


300
190
180
130
100
90
37
33
50
74
300
190
300
85
160
50
60
35
50
190
130
37


- 5.5
4 5.5
5 5.5
15 5.5
25 5.5
35 5.5
5 5.5
15 5.5
15 5.5
15 5.5
- 9.4
4 9.4
- 11.1
15 5.5
4 5.5
15 5.5
4 5.5
15 5.5
4 5.5
4 5.5
15 5.5
5 5.5


isothermss)


23-25
23-25
23 25
23-25
23-25
23 25
23-25
23-25
23 25
23-25
23-25
23-25
23-25
40
40
40
40
40
40
23 25
23 25
23-25


416
418
418
420
420
420
415
418
420
420
416
416
414
419
417
415
415
415
415
416
418
418


* Area of the chromophore and diluent as determined from Figure 3.5
** Corresponding pressure from Figure 3.5 isothermm)
*** pH of nano-pure water from filtration system is about 5.5













0.04- -- -300 A molecule"






0.002 \\ -

350 400 450 500 550 600
Wavelength (nm)


Figure 3.11: Transmission UV-vis of PdP4 films transferred at high and low MMA.
Absorbance scale corresponds to the film transferred at 300 A2 molecule'. The
absorbance for the film transferred at 130 A2 molecule-' has been divided by 10.

As the pH was raised, the amphiphiles became slightly more water-soluble and

the monolayer was increasingly susceptible to creep. However, films ofPdP4

compressed to 300 A2 molecule-1 were deposited onto zirconated ODPA templates

from subphases of pH 9.4 and 11.1. As the pH increased, Xmax of the Soret Band of

the transferred film decreased to 414 nm for the film deposited at pH 11.1. This was

the lowest value of Xmax, and therefore, the least aggregated LB transferred film of

PdP4. The Xmax of this Soret Band corresponds to that ofchromophore PdP4 in EtOH

at 10-12 M which is believed to be non-aggregated.

Consistently, D = 1 0.02 when measured at 0 incidence, indicating no

preferred in-plane orientation of the chromophore in the PdP4 and PdPI films.

However, in all films, D # 1 when measured at 45 o incidence. For films transferred at

high surface area, it is expected that the porphyrins should lie flat with all four

phosphonates tethered to the surface. Indeed, this is observed for films transferred at









190 A2 molecule-1 and 300 A2 molecule-' where the tilt angle, 0, with respect to the

surface normal is observed to be 90. Interestingly, the porphyrins also appear to lie

parallel to the surface in the films transferred at 130 A2 molecule-' where 0 is also

measured as approximately 90 o. This result implies that in films transferred at areas

smaller than the MMA of the flat porphyrin macrocycle, the molecules overlap,

stacking in bilayers or multilayers but with very little change in the tilt angle. There is

a larger uncertainty, possibly 10 in the measurement as the tilt angles near 90 0;26

however, these results confirm that the chromophores are lying approximately flat in

all of the films in this study.

Multilayers of the alternating ODPA/Zr/PdP4 films can be deposited and X-ray

diffraction confirms the layered nature of the films. Two or three orders of the (001)

Bragg peaks can be observed in each case. Films transferred at 190 A2 molecule-'

have a bilayer thickness of 42 A, which is smaller than the 48 A thickness seen in pure

ODPA/Zr/ODPA bilayers,28 suggesting that the 18-carbon tethers of PdP4 are not

fully extended in the alternating films. For the film transferred at 130 A2 molecule-,

the bilayer thickness increases to 47 A as the tetrasubstituted chromophores begin to

overlap.

Symmetric bilayers of PdP4/Zr/PdP4 fabricated according to Figure 2.2, were

also studied. Porphyrin PdP4 could be transferred on the down stroke onto a

hydrophobic substrate under a variety of conditions. After zirconation, deposition of a

capping layer of PdP4 results in a symmetric bilayer. The Soret Band is very similar

to that from alternating films deposited at the same area per molecule, and polarized

UV-vis indicates the porphyrins are also lying parallel to the surface. However, the

layers are poorly organized, as (001) Bragg peaks could not be seen in diffraction from









9-bilayer films. It is probably poor organization in the template layer ofporphyrin

PdP4 that is responsible for the lack of a well-defined layered structure.38

Mixed monolayers of PdP4 with ODPA were transferred onto ODPA templates

at different points along the surface pressure vs. area isotherms as shown in Table 1,

and the aggregation of the porphyrin in the transferred film parallels that seen in the

films of the pure porphyrins. For films transferred at pressures of 15 mN m-1, the

Soret Band appeared at 420 nm, shifting to 415 nm when transferred at pressures less

than 5 mN m-1 which, again, corresponds to the non-aggregated form seen in EtOH.

In all cases, polarized UV-vis indicates that the porphyrins orient parallel to the

surface.

The mixed monolayers show an interesting effect with increased temperature.

A mixed monolayer of 10% PdP4 with ODPA transferred at 15 mN m-' on a subphase

heated to 40" C shows a Soret Band max of 415 nm, shifted from 420 nm for the same

film deposited at room temperature. As the subphase is heated, the aggregates appear

to break-up in the mixed film. A similar effect is not seen on the pure films of PdP4.

It appears that the ODPA plays a role in breaking up the aggregated domains at higher

temperatures.

Films of PdP4 were also prepared by the SA technique. After the zirconated

ODPA template had been exposed to a PdP4 solution in EtOH/H20 for 2 hr, the

porphyrins were successfully incorporated into these films. The Soret Band appeared

at 414 nm, which then shifted to 411 nm after 60 min rinsing in hot CHC1. The Xmx

in the SA film was the closest of any of the PdP films to that seen in the dilute

solution. Therefore, it appears that non-aggregated assemblies of PdP4 are easily

obtained by self-assembly (Figure 3.12). However, the overall absorbance intensity of

these non-aggregated films is lower than observed in the films transferred by the LB

technique at high MMA.
















0.010


B 0.005-


0.000

-0.005
350 375 400 425 450 475
Wavelength (nm)


Figure 3.12: UV-vis of SA PdP4 films rinsed in hot CHCl3.



3.2.3.2. Films of compound PdP1. The H-A isotherms and the reflectance

UV-vis experiments described above indicate that the molecules of PdP1 aggregate

upon spreading, and this aggregation is preserved in the transferred films. In contrast

to PdP4, the monophosphonate PdPI is only slightly influenced by attempts to break

up the aggregates by changing the deposition conditions. The UV-vis spectrum of a

capping layer of PdP1 transferred at 52 A2 molecule-1 (12 mN m-1) is shown in Figure

3.13, where the Soret Band appears at 426 nm, consistent with the value observed in

the reflectance spectrum taken from the water interface. The shape of the Soret Band

does not change for films deposited at higher MMA, higher temperatures, or in

mixtures with ODPA. The peak position shifts only slightly (Table 2). The

orientation of the chromophores were also unaffected by the deposition conditions.

Polarized spectra consistently give tilt angles of 900, corresponding to the porphyrins

lying flat.


















0.04


0.02 -


0.00 l%

400 500 600
Wavelength (nm)



Figure 3.13: Transmission UV-vis of films of PdP 1 transferred at high and low
MMA.


X-ray diffraction from alternating films ofPdPI transferred at 52 A2

molecule-1 onto a zirconated ODPA template gives a layer thickness of 61 A (Table

3.2). This thickness is larger than that of the alternating films of ODPA/Zr/PdP4 or

ODPA/Zr/ODPA bilayers.28 Since optical spectroscopy indicates the molecules lie

flat, the enhanced thickness of the layer suggests they transfer as stacked bilayers or

multilayers. Further evidence for this arrangement comes from the film stability

studies, described below, which indicate that part of the transferred film of porphyrin

PdPI is physisorbed to the surface.









Table 3.2: UV-vis data from symmetric and alternating films ofPdPl. X, is given
for monolayers, and interlayer thickness is given for multilayers of films transferred
under a variety of transfer conditions.

Film Area of HI of Temp X. (nm) thickness
Transfer Transfer (C) (A)
(A2/molecule)* (mN/m)


OPA/Zr/PdPI
OPA/Zr/PdPI
OPA/Zr/ PdP1
OPA/Zr/ PdP 1
OPA/Zr/ PdP1
OPA/Zr/10%
PdPI
OPA/Zr/25%
PdP1
OPA/Zr/50%
PdPI
OPA/Zr/ PdP 1
OPA/Zr/ PdP1
OPA/Zr/ PdP 1
OPA/Zr/ PdPI
OPA/Zr/10%
PdP1
OPA/Zr/10%
PdPI
OPA/Zr/25%
PdPI
PdP1/Zr/ PdPI
10% PdP1/Zr/
10% PdPI


73
52
41
38
36
27


30


38


300
190
300
73
30


26


30


52
26


23-25
23 25
23-25
23 25
23 25
23-25


12 23-25


12 23-25


23-25
23-25
23-25
40
40


40


40


23-25
23-25


426
426
428
428
428
426


426


426


416
416
414
424
424


425


424


426
426


* Area of the chromophore and diluent as determined from Figure 3.7 isothermss)
** Corresponding pressure from Figure 3.7 isothermm)
*** pH ofnano-pure water from filtration system is about 5.5











3.2.3.3. Film stability. Zirconium phosphonate LB films are insoluble in

organic solvents due to the cross-linking within the zirconium-phosphonate extended

network.28 In order to monitor how well the porphyrin layers bind to the zirconated

template, transferred films of PdP4 and PdPI were rinsed with chloroform in a Soxhlet

extractor. Figure 3.19 shows the Soret Band absorbances as a function of washing

time in hot CHCl3. Figure 3.14 shows that none of the film of PdP4 is washed away

after 1 hr in chloroform, suggesting that all of the molecules are tethered to the

zirconated ODPA template. The same result was obtained for films of PdP4 deposited

at both higher and lower pressures or in mixtures with ODPA.

In contrast, the absorbance of the LB films of PdP1 exposed to CHC13

decreased significantly due to the desorption ofchromophores. The absorbance

leveled off after 20 min, to a value corresponding to the truly surface confined

chromophores (Figure 3.14). This result suggests that the stacked layers of

chromophores in the porphyrin PdPI films were partially physisorbed on the surface.



0.125-

0.100

0.075 a
-o
^ 0.050
< ~xS>


Time in Soxhlet (min)


Figure 3.14: Absorbance of Soret vs. time rinsed in hot CHCl3: a) PdP4, b) PdP1.











3.3. Conclusions


The behavior of the monosubstituted and tetrasubstituted porphyrins is very

different on the water surface, and the differences are carried over to the transferred

films. Porphyrin PdPI spreads on the water surface to a limited extent. Our proposal

for how the molecules behave on the water surface is shown schematically in Figure

3.15. Optical spectroscopy indicates that PdPI aggregates, but the nr-A isotherm and

X-ray diffraction from the transferred layers suggest that the aggregates are only a few

molecules thick. The aggregates are present at both high and low MMA and can be

transferred, as aggregates, onto the zirconated ODPA templates. Some molecules

from each aggregate chemisorb to the zirconated surface through zirconium

phosphonate linkages, but some are physisorbed as part of the preformed aggregates.

When exposed to hot chloroform, the physisorbed part of the film is dissolved away.



50 I



S30

120 'T .

10 "1--

0
20 40 60 80 100 120 140
MMA (A2 molecule)



Figure 3.15: Illustration of orientation and packing of PdP films transferred at high
and low MMA.









Chemical modification with four alkylphosphonic acid sidegroups allows the

porphyrin to spread completely. Porphyrin PdP4 spreads to a monolayer thick film at

high MMA, and as the film is compressed, an increase in surface pressure is registered

near 200 A2 molecule-1, corresponding to the area of the flat porphyrin macrocycle.

However, the side-by-side arrangement of the porphyrin chromophores is not stable as

the pressure is increased and the film rearranges, with the molecules sliding over one

another to form multiple chromophore layers. This behavior is illustrated in Figure

3.16.




50

40



S20

10-

0-
50 100 150 200 250
MMA (A2 molecule)



Figure 3.16: Illustration of orientation and packing of PdP4 films transferred
at high and low MMA.


The films of PdP4 can be transferred at high MMA onto zirconated ODPA

templates to form monolayer or submonolayer films of the porphyrin chemisorbed to

the surface with the chromophore ring oriented parallel to the surface. Films of PdP4

can also be transferred at lower MMA, where the reflectance UV-vis indicates the









porphyrins are interacting. Analysis of the transferred films suggests that the

porphyrin chromophores are lying flat and overlapping each other to form layers that

are a few molecules thick. In contrast to the films of PdPI, all of the molecules in the

aggregated films ofPdP4 appear to be chemisorbed to the surface. None of the film is

lost during rinsing with hot chloroform. The different behavior probably results from

the fact that four phosphonic acid groups increase the chance of each molecule

bonding onto the zirconium phosphonate network. Any orientation of the porphyrin

macrocycle will direct at least one alkylphosphonic acid side chain toward the surface.

Also, all of the phosphonic acids have the potential to reach the water surface at high

MMA. Forcing a strongly hydrophilic group off of the water surface requires more

energy than reorganization of the alkyl chains or shifting the chromophore

interactions.

Whether the Langmuir monolayers are transferred intact or reorganized during

film transfer is not yet completely clear. At high MMA, molecules of PdP4 lie flat on

the water surface and this arrangement appears to be preserved in the transferred films

based on the similar m~,. However, when the films are transferred at lower MMA,

where the films are clearly aggregated, there could be some rearrangement. There is a

significant driving force for forming zirconium phosphonate linkages, and the

aggregates could rearrange during transfer to further maximize interactions with the

zirconated surface. While the porphyrins are clearly oriented parallel to the surface in

the transferred film, providing each porphyrin the chance to form multiple zirconium

phosphonate bonds, it is not known if the molecules aggregate the same way on the

water surface.

The LB procedure used in these studies takes advantage of the binding energy

of the zirconium phosphonate continuous network and is shown to be quite versatile.

Both symmetric and alternating layer films can be prepared. Use of the zirconated









ODPA template layer allows almost any phosphonic acid derivatized amphiphile to

transfer in a capping layer.28,38,65,125 Unlike conventional LB depositions, films of

PdP4 and PdPI can be transferred onto the zirconated template layers at any surface

pressure, allowing, in the case of PdP4, the arrangement of the molecules in the

transferred films to be tuned by choice of the area-per-molecule at deposition. The

films do not need to be stable Langmuir monolayers in order to transfer, as the driving

force is formation of the zirconium phosphonate bonds. It is the strength of the

zirconium phosphonate interaction, in particular the lattice energy associated with the

zirconium phosphonate extended network, that is responsible for the exceptional

stability of these non-traditional LB films.28,38

Zirconium phosphonate LB films, like solid-state zirconium phosphonates, are

insoluble in organic solvents and under most aqueous conditions. The inorganic

network has also been shown to enhance the thermal stability of LB films.126 The

zirconium phosphonate inorganic extended network adds substantial stability to the

films, which are insoluble under most organic and aqueous conditions. The methods

developed here with the palladium tetraphenyl porphyrins can also be applied to other

porphyrin systems, and in this way the vast array of physical and chemical
characteristics of porphyrins, including catalytic activity, should be able to be

incorporated in stable LB films.












CHAPTER 4
MANGANESE PORPHYRIN CONTAINING
ZIRCONIUM PHOSPHONATE THIN FILMS


4.1 Background


Monolayer and film work using the molecule manganese 5,10,15,20-

tetrakis(2,3,5,6-tetrafluorophenyl-4-octadecyloxyphosphonic acid)porphyrin, or

MnP4, will be discussed in Chapter 4 (Figure 4.1A). For comparison, work done

using a similar molecule without the four alkylphosphonic acid chains, manganese

5,10,15,20-tetrakis(penta-fluorophenyl)porphyrin, or MnPO, will also be discussed

(Figure 4.1B). The manganese porphyrins are structurally and chemically more

complex than the palladium porphyrins. The Mn(III) central metal is a 5- or 6-

coordinate d4 metal.80,127,128 Depending on the ligand character, Mn(III) is either S =

2 (high spin) or S = 1 (low spin).129 Also, depending on the axial ligand or ligands,

the Mn(III) may or may not be co-planar with the porphyrin ligand. Mn(III) also has

an easily accessible lower oxidation state, which leads to significant metal/porphyrin

electronic interactions,80 the Mn(III)-porphyrins have a tendency to form face-to-face

dimers bridged through an axial ligand,130 and the Mn(III)-porphyrins are vulnerable

to demetallation under certain conditions. Therefore, film characterization using these

molecules was much more complicated than with the Pd-porphyrins.

To investigate the catalytic properties of manganese-porphyrin films, film

preparation procedures involving the tethering of Mn-porphyrins to a metal








phosphonate network were developed. This method involves the initial formation of a
zirconated octadecylphosphonic acid (ODPA) template onto which a film of pure
MnP4 can be SA or transferred via the LB technique (Figure 2.2). Including MnP4 in
a zirconium phosphonate network provided films that were stable toward harsh
organic conditions. Also, the strong oxophilicity of the zirconium for the phosphonate
oxygens enabled the film preparation procedure to be easily altered and fine tuned and
complete film characterization to be carried out.



A O(CH 2)18PO 3H2 (R) B F
F F F F
I c II
F F F F



F /)<.^ F F F F F



R F


Figure 4.1: Structures of A) MnP4 and B) MnPO.


The MnP4 molecule is similar to the PdP4 molecule described in Chapter 3, in
which the manganese tetraphenylporphyrin (MnTPP) chromophore and the strongly
hydrophilic phosphonate groups are separated by 18-carbon chains (Figure 4.1 A). This
geometry allowed for the porphyrin to be sitting at the exterior of the film and
available for catalysis while the phosphonates were buried in the hydrophilic region
and available for binding to the stabilizing inorganic network. The incorporation of
this network significantly improves the resistance of the film to typically destructive









forces such as solvent, heat, or time.126 In addition, having four amphiphilic chains on

the porphyrin permits the formation of Langmuir monolayers of these materials

without diluting the amphiphiles with a good film forming amphiphile such as stearic

acid.33,88-90

The MnP4 films were first investigated on the water surface in a Langmuir

monolayer. An isotherm of this material showed significant film compressibility

(Figure 4.2). Reflectance UV-vis showed that the porphyrins formed face-to-face

dimers above ca. 10 mN m"', which were maintained upon transfer onto glass

substrates.

The procedure for MnP4 film formation was directed by the film

characterization results. In most cases, evidence suggests that the phosphonic acid

tethers on the porphyrins were able to bind to the metal phosphonate lattice. Film

stability was monitored by UV-vis, which displayed no significant chromophore loss

after 5 minutes in hot CHCl3 or CH2Cl2. Although the zirconium phosphonate lattice

contributes no interesting physical phenomena to the final film, the strong oxophilicity

of the phosphonate oxygens for the zirconium lattice allow for a wide variety of stable

films to be formed.


4.2 UV-vis Behavior of MnTPPs


4.2.1. Solution Studies

Both MnTPPs displayed electronic behavior in solution consistent with d-type

hyperporphyrins. Mn(II)-porphyrins have absorption spectra similar to free-base

porphyrins due to a lack of metal-porphyrin interaction; however, the absorption

spectrum of the Mn(III)-porphyrin is quite different. According to Gouterman,80

Mn(III)TPP is a classic d-type hyperporphyrin with extra absorption bands at higher









energies relative to max. The MnP4 and MnPO with chloride axial ligands are

spectrally consistent with d4 porphyrins in high-spin configurations.131 The strong

absorption near 450-485 nm is often called Band V, due to the fact that this transition

is not pure 7t-n* in nature but includes metal-porphyrin orbital mixing. However,

traditionally, it is still often called the Soret Band.80 One strong band commonly seen

to the blue of the Soret Band is called Band VI. A prominent peak, often observed

specifically in the MnP4 UV-vis spectrum ca. 410 nm, is referred to as Band Va.

Ligand effects and orientation or aggregation effects are reflected primarily in

the shape or shift of the Soret Band and in the extinction coefficient (e).132 Therefore,

the behavior of this band was carefully monitored. Also, different solvents used for

porphyrin investigations caused changes in the absorption spectra. If a coordinating

solvent was used, the axial ligand was displaced by a solvent molecule causing a shift

in the Soret Band and in the V/VI intensity ratio.80,132

4.2.1.1. UV-vis of MnPO in solution. A concentration study of MnPO in

CH2C12 showed that the Xmax was consistently at 475 477 nm between 10-5 and 10-8

M (8 = 1.25 x 107 M-' m-'). These results suggest that the MnPO chromophore had

little tendency to aggregate in these dilute solutions, and that the axial ligand was

probably chloride. 132 In EtOH, the max of the MnPO solution was also constant over

the same concentration range; however, the Soret Band was blue shifted to 454 456

nm. According to Mu, the coordination of two axial methanol ligands to a MnTPP

caused a 10 nm blue shift relative to the chloride bound moieties; therefore, it is

believed that this blue shift is due to bis-EtOH binding.133 Figure 4.2 shows the

solution UV-vis of MnPO in EtOH and CHC13 at 10" M. Not only is the Soret Band

shifted, but the ratio of Band V to Band VI has also changed, indicating a change in

the metallo-porphyrin ligand environment.




Full Text
59
R
0(CH2)18P03H2
R
A
B
Figure 3.1: Structures of A) PdP4 and B) PdPl.
Palladium polyhalogenated porphyrins were chosen based on the following
considerations. First, palladium porphyrins are not demetallated in acidic conditions,
and their diamagnetic character makes following the synthesis with NMR
spectroscopy possible. Second, manganese and iron polyhalogenated porphyrins are
well-known catalysts for the oxidation of hydrocarbons;123 therefore, if palladium is
replaced by one of these metals, the films can be used for catalytic applications.
Third, pentafluorophenyl substituents on porphyrins allow straightforward
functionalization of this ligand by aromatic nucleophilic displacement with an alcohol.
In addition, the ether bonds are more stable toward hydrolysis and less hydrophilic
than the ester or amide linkages usually used to tether alkyl chains on porphyrins.
High hydrophobicity of the linkage is a requirement because competition with the
polar phosphonic acid head-group should be avoided during the LB film preparation.


167
(59) Wang, R.-C.; Zhang, Y.; Hu, H.; Frausto, R. R.; Clearfield, A. Chem. Mater.
1992, 4, 864-870.
(60) Thomas, L. C.; Chittenden, R. A. Spectrochimica Acta 1970, 26A, 781-800.
(61) Lee, H.; Kepley, L. J.; Hong, H.-G.; Mallouk, T. E. J. Am. Chem. Soc. 1988,
110, 618-620.
(62) Lee, H.; Kepley, L. J.; Hong, H.-G.; Akhter, S.; Mallouk, T. E. J. Phys. Chem.
1988,92, 2597-2601.
(63) Cao, G.; Hong, H.-G.; Mallouk, T. E. Acc. Chem. Res. 1992, 25, 420-427.
(64) Fanucci, G. E.; Seip, C. T.; Petruska, M. A.; Ravaine, S.; Nixon, C. M.;
Talham, D. R. Thin Solid Films 1998, 327-329, 331-335.
(65) Petruska, M. A.; Fanucci, G. E.; Talham, D. R. Chem. Mater. 1998,10, 177-
189.
(66) Fanucci, G. E.; Petruska, M. A.; Meisel, M. W.; Talham, D. R. J. Solid State
Chem. 1999, 745,443-451.
(67) Petruska, M. A.; Talham, D. R. Chem. Mater. 1998,10, 3673-3682.
(68) Croney, J. C., Helms, M.K., Jameson, D.M., Larsen, R.W. J. Phys. Chem. B
2000, 104, 973-977.
(69) Hsiao, J.-S., Krueger, B.P., Wagner, R.W., Johnson, T.E., Delaney, J.K.,
Mauzerall, D.C., Fleming, G.R., Lindsey, J.S., Bocian, D.F., Donohoe, R.J. J.
Am. Chem. Soc. 1996,118, 11181-11193.
(70) Ishida, A.; Sakata, Y.; Majima, T. Chem. Lett. 1998, 267-268.
(71) Jolliffe, K.; Bell, T.; Ghiggino, K.; Langford, S.; Paddon-Row, M. Angew.
Chem. Int. E. 1998, 37, 916-919.
(72) Florsheimer, M., Mohwald, H. Thin Solid Films 1988,159, 115-123.
(73) Amini, M. K., Shahrokhian, S., Tangestaninejad, S. Analyst 1999,124, 1319-
1322.
(74) Arnold, D.; Manno, D.; Micocci, A.; Tepore, A.; Valli, L. Langmuir 1997,13,
5951-5956.
(75) Smith, V. C., Batty, S.V., Richardson, T., Foster, K.A., Johnstone, R.A.W.,
Sobral, A.J.F.N., Rocha Gonzales, A.M.d'A. Thin Solid Films 1996, 284-285,
911-914.
(76) Schenning, A.; Hubert, D.; Fetters, M.; Nolte, R. Langmuir 1996,12, 1572-
1577.


78
32.3.3. Film stability. Zirconium phosphonate LB films are insoluble in
organic solvents due to the cross-linking within the zirconium-phosphonate extended
network.28 In order to monitor how well the porphyrin layers bind to the zirconated
template, transferred films of PdP4 and PdPl were rinsed with chloroform in a Soxhlet
extractor. Figure 3.19 shows the Soret Band absorbances as a function of washing
time in hot CHC13. Figure 3.14 shows that none of the film of PdP4 is washed away
after 1 hr in chloroform, suggesting that all of the molecules are tethered to the
zirconated ODPA template. The same result was obtained for films of PdP4 deposited
at both higher and lower pressures or in mixtures with ODPA.
In contrast, the absorbance of the LB films of PdPl exposed to CHCI3
decreased significantly due to the desorption of chromophores. The absorbance
leveled off after 20 min, to a value corresponding to the truly surface confined
chromophores (Figure 3.14). This result suggests that the stacked layers of
chromophores in the porphyrin PdPl films were partially physisorbed on the surface.
Figure 3.14: Absorbance of Soret vs. time rinsed in hot CHC13: a) PdP4, b) PdPl.


86
energies relative to Xmax. The MnP4 and MnPO with chloride axial ligands are
spectrally consistent with d4 porphyrins in high-spin configurations.131 The strong
absorption near 450-485 nm is often called Band V, due to the fact that this transition
is not pure n-n* in nature but includes metal-porphyrin orbital mixing. However,
traditionally, it is still often called the Soret Band.80 One strong band commonly seen
to the blue of the Soret Band is called Band VI. A prominent peak, often observed
specifically in the MnP4 UV-vis spectrum ca. 410 nm, is referred to as Band Va.
Ligand effects and orientation or aggregation effects are reflected primarily in
the shape or shift of the Soret Band and in the extinction coefficient (s).132 Therefore,
the behavior of this band was carefully monitored. Also, different solvents used for
porphyrin investigations caused changes in the absorption spectra. If a coordinating
solvent was used, the axial ligand was displaced by a solvent molecule causing a shift
in the Soret Band and in the V/VI intensity ratio.80-132
4.2.1.1. UV-vis of MnPO in solution. A concentration study of MnPO in
CH2C12 showed that the X.max was consistently at 475 477 nm between 10-5 and 10'8
M (s = 1.25 x 107 M'1 m1). These results suggest that the MnPO chromophore had
little tendency to aggregate in these dilute solutions, and that the axial ligand was
probably chloride. 132 In EtOH, the A.max of the MnPO solution was also constant over
the same concentration range; however, the Soret Band was blue shifted to 454 456
nm. According to Mu, the coordination of two axial methanol ligands to a MnTPP
caused a 10 nm blue shift relative to the chloride bound moieties; therefore, it is
believed that this blue shift is due to bis-EtOH binding.133 Figure 4.2 shows the
solution UV-vis of MnPO in EtOH and CHC13 at 10-6 M. Not only is the Soret Band
shifted, but the ratio of Band V to Band VI has also changed, indicating a change in
the metallo-porphyrin ligand environment.


160
When experiments similar to the Bacciochi study with excess substrate were
reproduced using 400 pmol cyclooctene and 80 pmol H202 in lmL of solution, with
25 pmol imidazole and 1 nmol of MnP added to the homogeneous reaction, very little
epoxide was detected in the blank or homogeneous reactions." Fortunately, a clear
increase in the yield was observed with the immobilized porphyrins (Table 6.6). As in
the PhIO reactions, the immobilized catalyst appeared to be relatively stable toward
the reaction conditions (Figure 6.7).
Table 6.6: Conversion of cyclooctene to cyclooctene oxide with 400 pmol cyclooctene
and 80 pmol H202 in lmL of solution using imidazole and porphyrin.
SA ImODPA/SA MnP4
Cyclooctene oxide
Yield
Blank
0.2%-0.3%
Homogeneous*
0.5%-1.0%
Films
12.6%, 12.8%
* Homogeneous solution contains 40 pmol ImH and lnmol of MnPO
The epoxidation of cyclooctene was also run in the presence of excess oxidant
with approximately the same molar ratio of catalyst (10 3 vs other reactants). The ratio
examined using excess oxidant was 80 ^mol cyclooctene to 400 pmol H202. The
results were surprising in one aspect. After the 24 hr catalysis reaction was concluded,
the UV-vis of the film showed nearly complete demetallation of the porphyrin (Figure
6.8).


37
immobilized on an ion-exchange resin support showed significant increases in
catalytic activity in the presence of either imidazole or 4-methylimidazole. With the
heterocyclic ligand present, nearly quantitative conversion of cyclooctene to
cyclooctene oxide was achieved, relative to only 5% conversion in the absence of
imidazole over the same time period.112 Likewise, Arasasingham et al. found a 4 to
10 fold increase in the rate of the reaction between a manganese porphyrin and an
oxygen source commonly used in olefin epoxidation reactions, t-BuOOH, in the
presence of imidazole. Since the oxidation of the porphyrin accelerates, a rate increase
should also be observed in the overall epoxidation reaction.98
According to Yuan and Bruice, the reaction of the Mn(III)TPP Cl complexes
with peroxide oxidants only proceeds in the presence of a heterocyclic nitrogen base
ligand such as imidazole or pyridine. The imidazole ligation was pH dependent and
was evident only above pH 5. Consequently, the enhanced oxidation rate was also pH
dependent. Further, with common oxidants, nitrogen base ligation led to a significant
increase in the oxygen transfer rate.111
The rate increase could be due to a general-base catalysis and/or ligation of the
imidazole (ImH) to the manganese ion.98 Activation by ligation of ImH is supported
by the fact that when 2,4,6-trimethyl-pyridine is used as the base, which is sterically
forbidden from porphyrin ligation, no increase in the reaction rate was observed.
However, when the ImH concentration was below a saturation level, the rate increase
was linear with ImH concentration up to a saturation level. An increase in the
oxidation rate with a basic ligand is likely due to the increase in the electron density at
the metal center arising from donation of the lone pair of electrons from the ImH.98
The presence of the ImH as an axial ligand has been shown also to stabilize the metal-
oxo compound.99


163
6.3 Conclusions
From the above results, it appears that the immobilization of the porphyrins does
slightly improve the catalytic efficiency of the Mn-porphyrin with PhIO as the
oxidant. An improvement is also observed in the catalyst stability in the zirconium
phosphonate films relative to the homogeneous and previous LB film examples. The
stability and easy recovery of these immobilized porphyrins is an advantage over
previous literature cases.
The improvement of the epoxide yields using H202 using the immobilized
porphyrin and imidazole did show promise when the molar ratio was ca. 400 pmol
cyclooctene to 80 pmol H202 to 1 nmol of catalyst. Additionally, these films appeared
to be significantly more stable over 24 hr than the homogeneous catalysts.
Unfortunately, with excess oxidant, the Mn-porphyrin in the film completely
demetallates.
Overall, zirconium phosphonate templates allowed the successful incorporation
of both catalytic porphyrins and imidazoles into thin film environments. The
inorganic template also introduced significant film stability and overall improved the
catalytic efficiency of the immobilized catalysts.


43
The amphiphiles are shown in Figure 2.1 as gray circles, representing the
hydrophilic head group, and black lines, representing the hydrophobic tails. The
subphase, which is usually aqueous, must be nanopure. Because there is such a small
amount of amphiphile present, the monolayer is extremely sensitive to contaminants -
especially lipids and other surfactants and ions found in soaps and tap water.
The barriers compress the amphiphiles at a constant speed. In studying the 1T-
A isotherm, the film is compressed until it collapses. For LB transfers, the film is
compressed until the desired transfer pressure is achieved. At this point, the
monolayer is held at constant pressure for approximately two minutes until the
monolayer is stabilized, then the solid substrate is dipped vertically down through this
monolayer.
The monolayers are first characterized with IT-A isotherms. In modem
computer operated systems, the concentration (mg mL'1) and the molecular weight (g
mol'1), or the concentration in mol L'1, of the compound being spread is entered into
the program along with the spreading surface area in mm2. From this information, the
program can calculate the MMA in 2 molecule '. As the barriers move together and
the surface is compressed, the effective MMA is decreased and the surface pressure
increases.
The preparation of the zirconium phosphonate porphyrin films took place by a
three-step deposition procedure (Figure 2.2).28>29>38 A glass sample vial was placed in
the subphase in the well of the trough. Octadecylphosphonic acid was spread from 0.3
mg mL-1 CHCI3 solutions and compressed at 15 20 mm min-1 on the water surface.
At 20 mN m'1, the substrate was dipped down through the monolayer surface and into
the sample vial at 8 mm min"1, transferring the ODPA template layer. The substrate
and the vial were then removed from the trough and an amount of zirconyl chloride
was added to the vial to make the solution ca. 4 x 10"5 M in ZH+. After 20 min in the


52
reactions. Even under relatively harsh conditions such as elevated temperatures or
rapid solvent flow, the porphyrins films appeared to be stable. Additionally, the
zirconium phosphonate network made preparation of the MnP4-imidazole films
possible by a wide variety of mechanisms.
MnP4 and ImODPA could be incorporated into both LB and SA films. In
order to accommodate ImODPA into LB films, two types of spreading solutions were
used: 1) ImODPA mixed with a stabilizing agent such as hexadecylphosphonic acid
(HDPA), or 2) ImODPA mixed with the MnP4 amphiphile. Alone, the ImODPA did
not form sufficiently stable monolayers for transfer. The porphyrin, MnP4 was
substituted into the films of pure ImODPA or ImODPA/HDPA from an EtOH/H20
solution. Alternatively, the MnP4 film was transferred by the LB technique and then
the ImODPA was substituted into these films.
First, in the case of the mixed 25% ImODPA/75% HDPA films, 200 pL of a
solution with a weighted average concentration of 0.17 mg/mL and a weighted average
molecular weight of 329.86 mg mmol'1 was spread on the water surface and
compressed to 12 mN m'1. The film was transferred at 5 mm min'1 on the upstroke
completing the zirconium network. Films made in this way were abbreviated
ODPA/Zr/25% ImODPA. These films were then placed in a solution of the MnP4 at
ca.10'5 M in 9/1 EtOH/H20 and the porphyrin phosphonic acids were allowed to
substitute into the defect or vacant sites in the film for 2 hr. Transmission UV-vis of
these films confirms the ability to include the porphyrins by this method, and the
resulting films were called ODPA/Zr/25% ImODPA, SA MnP4.
Films containing both the MnP4 and the ImODPA transferred by the LB
technique from a mixed monolayer were also prepared. A 70/30 mixture of
MnP4/ImODPA, respectively, was dissolved in CHC13 with a weighted concentration
and MW of 0.289 mg/mL and 992.70, respectively. 175 pL of this solution was


84
phosphonate network were developed. This method involves the initial formation of a
zirconated octadecylphosphonic acid (ODPA) template onto which a film of pure
MnP4 can be SA or transferred via the LB technique (Figure 2.2). Including MnP4 in
a zirconium phosphonate network provided films that were stable toward harsh
organic conditions. Also, the strong oxophilicity of the zirconium for the phosphonate
oxygens enabled the film preparation procedure to be easily altered and fine tuned and
complete film characterization to be carried out.
Figure 4.1: Structures of A) MnP4 and B) MnPO.
The MnP4 molecule is similar to the PdP4 molecule described in Chapter 3, in
which the manganese tetraphenylporphyrin (MnTPP) chromophore and the strongly
hydrophilic phosphonate groups are separated by 18-carbon chains (Figure 4.1 A). This
geometry allowed for the porphyrin to be sitting at the exterior of the film and
available for catalysis while the phosphonates were buried in the hydrophilic region
and available for binding to the stabilizing inorganic network. The incorporation of
this network significantly improves the resistance of the film to typically destructive


39
containing films to reaction conditions and to allow these films to be recycled in a
number of catalytic studies. Chapter 2 is an overview of the experimental techniques
used to prepare and characterize the films described in this dissertation, and materials
and instrumentation used in this pursuit are also presented.
Films containing a Pd-tetraphenyl porphyrin were prepared to develop film
preparation procedures and to better analyze the UV-vis properties of porphyrin
containing films. Substituted tetraphenyl porphyrins, palladium 5,10,15,20-
tetrakis(2,3,5,6-tetrafluorophenyl-4-octadecyloxyphosphonic acid)porphyrin (PdP4)
and palladium 5,10,15-tris(2,6-dichlorophenyl)-20- (2,3,5,6-tetrafluorophenyl-4-
octadecyloxyphosphonic acid)porphyrin (PdPl), have been studied as Langmuir
monolayers and as zirconium phosphonate LB and SA films.
Films were prepared incorporating the pure porphyrins and the porphyrins
mixed with octadecylphosphonic acid (ODPA). The Langmuir monolayers were
characterized with pressure vs. area isotherms and reflectance UV-vis spectroscopy.
Using a three-step deposition technique, symmetric and alternating zirconium
phosphonate bilayers and multilayers were prepared by the LB technique. PdP4
containing films were also prepared by the SA technique. In all PdPl and PdP4 films,
the porphyrin constituent resided in the hydrophobic region of the monolayer and the
phosphonate substituents bound zirconium ions in the hydrophilic region.
LB and SA films were studied with transmittance UV-vis and the LB films
were further investigated using X-ray diffraction. Control over chromophore
interaction was achieved by chemical modification of the amphiphiles and by selection
of appropriate transfer conditions. For example, reduced aggregation was seen in LB
films of the tetraphosphonic acid substituted porphyrin PdP4 transferred at mean
molecular areas (MMA) larger than the area per molecule of the substituted porphyrin
and in SA films. In these films, the porphyrin macrocycles are non-aggregated and


CHAPTER 2
EXPERIMENTAL
2.1 Langmuir-Blodgett and Self-Assembled Films
2.1.1. General Langmuir-Blodeett and Self-Assembly Procedures
2.1.1.1. Film Formation. The general procedure for forming LB films starts
with the Langmuir monolayer, which are prepared on a Langmuir trough. The trough
consists of a rectangular piece of Teflon, typically 1 cm deep, supported on a metal
base with Teflon barriers, shown as black rectangles in Figure 2.1. A Teflon well is
carved in the center of a double barrier trough for transferring monolayers. The
spreading solution is prepared by dissolving the amphiphile of interest in a volatile
solvent, such as CHCI3. The solution is carefully applied to the subphase surface,
ideally spreading the molecules uniformly over the surface.
i Syringe
Wilhelmy
Balance
Surfactant
molecule
Teflon Trough
Wilhelmy
Plate
Figure 2.1: Schematic of Langmuir-Blodgett trough and monolayer.
42


25
Figure 1.11: Structures of porphyrin-type molecules A) porphine B) free base
porphyrin, and C) pthalocyanine.
Porphyrins have characteristic and strong optical transitions by which they can
be identified. The bands often observed in visible spectra of porphyrins include the B
or Soret Band and Q Bands, as seen in Figure 1.12 for a palladium
tetraphenylporphyrin (PdTPP). The Soret Band is associated with the allowed %-n*
transition and is typically seen between 380 and 420 nm.80
Figure 1.12: UV-vis spectrum of a metallo-porphyrin (PdTPP).


130
After sitting overnight, the red chloride peak again emerged. This behavior is
contradictory to results obtained previously where the chloride peak seemed to
disappear with time. By adding a sufficient amount of chloride to fill the porphyrin
axial positions, the phosphonic acids may be forced to bind to the zirconium network.
The chloride axial binding is in equilibrium while the zirconium-phosphonate binding
is not. Once the phosphonates are unavailable for ligation, the imidazole binding,
which is evidenced by a blue shifted Band Vi, is more likely to be observed. Further
proof of imidazole binding is in Band Va, which was earlier associated with
phosphonic acid binding causing the demetallation of the Mn-porphyrin. This band
was clearly absent in these films.
5.3.3. Self-assembling the MnP4 and ImODPA from a mixed solution
As an alternative method, a self-assembly solution of a 70/30 mixture of the
ImODPA and MnP4 was prepared. The UV-vis of this mixed SA solution showed
Band Vi at 460 and Band Vii at 477 (Figure 5.14). Band Vi in solution may represent
phosphonic acid binding; however, as the film was formed these phosphonic acids
were attracted to the zirconium network leaving the manganese available for binding
the imidazole. The blue shift may also demonstrate some contribution from porphyrin
aggregation. Rinsing with a hot solvent was consistently done to remove any
physisorbed chromophores from these films, though in some cases, as shown in Figure
5.14, there often was very little loss in absorbance intensity overall indicating that
there were few physisorbed chromophores present initially.


145
investigated under condition B, 40:20:200:1 cyclohexene to imidazole to H202 to
catalyst, with the same porphyrin gave epoxide yields of ca. 91%. When the catalyst
was MnTFPP(Cl), called MnPO in our studies, the yields were 58% under conditions
A and 74% under conditions B. The porphyrins containing halide substitutents on the
phenyl rings appeared to be fairly resistant to bleaching over the course of the
homogeneous reactions.
Baciocchi et al. studied the homogeneous epoxidation of cyclooctene to
cyclooctene oxide using both manganese and iron porphyrins as catalysts, comparing
the effects of electron donating vs. electron-withdrawing substituents on the
tetraphenyl rings." The porphyrins studied included 5,10,15,20-tetrakis(2,6-
dimethoxyphenyl)porphyrin (MnTDMeOPP(Cl)), the above MnTDCP(Cl), and
5,10,15,20-tetraphenylporphyrin (MnTPP(Cl)). Results indicate that MnTPP(Cl), in a
1:40:200 ratio to substrate and hydrogen peroxide gave epoxide yields of 15% as
referenced to the initial substrate concentration. The MnTDCPP(Cl) derivative in the
same molar ratio to substrate and oxidant gave a 36% yield (as compared to 91% in
the Battioni report), and the MnTDMeOPP(Cl) catalyst gave a 78% yield.
When the oxidant was instead iodosylbenzene, or PhIO, the substrate was used
in excess with a molar ratio of 1:400:20, porphyrin to substrate to PhIO, respectively.
The epoxide yields ranged from 73 to 80% with reference now to the oxidant. In both
the PhIO and H202 epoxidation reactions, the bleaching effects observed with the
MnTDCPP(Cl) and MnTDMeOPP(Cl) catalysts were mild, under 5%. Only the
unsubstituted MnTPP(Cl) showed up to 10% bleaching reported over the course of the
2 hr reaction in the presence of PhIO.
Thin films of catalytic porphyrins have also been studied. Abatti et al.
investigated LB films containing an iron(III) 5, 10, 15, 20-tetrakis(tetradecyl-2-N-
pyridyl) porphyrin. With the inclusion of alkyl chains on the four-pyridine rings, clear


CHAPTER 1
INTRODUCTION
1.1 Ultrathin Films
The study of ultrathin films, especially monomolecular thick films, enables the
study of two-dimensional systems and allows the simplification of complicated
thermodynamic behaviors. Recent interest in monolayers and multilayers focuses on
the many potential applications of organized and functional thin films, which include
optoelectronics,1-3 coatings,4'7 chemical sensors, f68-10 and heterogeneous
catalysts.11'13 In order to prepare these organized and essentially two-dimensional
structures, the Langmuir-Blodgett (LB) and self-assembly (SA) techniques have been
developed.
The study of monolayer thick films began long before the early twentieth
century investigations of Irving Langmuir and Katharine Blodgett. It is believed that
centuries ago drops of oil were used to calm waves in ponds and other small bodies of
water.14-13 Benjamin Franklin studied monolayers of oil on the surface of a pond.
Agnes Pockels pioneered the study of a monolayer on the water surface in the
laboratory environment, and is credited with building the first trough.15 However, the
first systematic study of monolayers of amphiphilic molecules on aqueous surfaces
began with Irving Langmuir's studies at GE Laboratories and, hence his name is
associated with a fundamental method of preparing organized, monomolecular thick
1


47
and bromide) (Aldrich), and imidazole with no alkyl substituents (ImH) (Kodak). A 1
cm x 1 cm x 3 cm quartz cuvette held the sample, and the background using the
corresponding pure solvent was subtracted.
A Teflon substrate holder with grooves cut at 45 to one another was used to
obtain sampling at 0 (beam normal to the substrate) and 45 incidence to the substrate
surface. A plane, visible polarizer was used to select s- and p-polarized light.
Reflectance UV-vis experiments were performed on a KSV 2000 mini-trough using an
Oriel spectrophotometer and a 77410 filter with a range from 200 600 nm.
2.1.2.2. X-ray Photoelectron Spectroscopy. X-ray photoelectron spectroscopy
(XPS) was performed on a Perkin-Elmer PHI 5000 Series spectrometer using the Mg
Ka line source at 1253.6 eV. The instrumental resolution was 2.0 eV, with anode
voltage and power settings of 15 kV and 300 W, respectively. The operating pressure
was around 5 x 109 atm. Survey scans were performed at a 45 takeoff angle with a
pass energy of 89.45 eV. During multiplex scans, 80 100 scans were run at each
peak over a 20-40 eV range with a pass energy of 37.35 eV.
2.1.2.3 X-rav Diffraction. In order to obtain low angle X-ray diffraction
(XRD) patterns, multilayer films were transferred onto a hydrophobic glass slide. The
diffraction patterns were obtained using a Phillips APD 3720 X-ray powder
diffractometer with the CuKa line, X = 1.54 , as the source for films ranging from 10
to 15 bilayers.
2.1.2.4. Attenuated Total Reflectance Infrared. Attenuated total reflectance
infrared spectroscopy was performed on a Mattson Instruments (Madison, WI)
Research Series-1 FTIR spectrometer equipped with a deuterated triglyceride sulfide
detector and a Harrick (Ossining, NY) TMP stage which held the Ge crystal substrate.
ATR-FTIR spectra consisted of 500 scans at 2 cm-1 resolution and were referenced to
the silanized crystal or previous bilayers.


81
porphyrins are interacting. Analysis of the transferred films suggests that the
porphyrin chromophores are lying flat and overlapping each other to form layers that
are a few molecules thick. In contrast to the films of PdPl, all of the molecules in the
aggregated films of PdP4 appear to be chemisorbed to the surface. None of the film is
lost during rinsing with hot chloroform. The different behavior probably results from
the fact that four phosphonic acid groups increase the chance of each molecule
bonding onto the zirconium phosphonate network. Any orientation of the porphyrin
macrocycle will direct at least one alkylphosphonic acid side chain toward the surface.
Also, all of the phosphonic acids have the potential to reach the water surface at high
MMA. Forcing a strongly hydrophilic group off of the water surface requires more
energy than reorganization of the alkyl chains or shifting the chromophore
interactions.
Whether the Langmuir monolayers are transferred intact or reorganized during
film transfer is not yet completely clear. At high MMA, molecules of PdP4 lie flat on
the water surface and this arrangement appears to be preserved in the transferred films
based on the similar A.max. However, when the films are transferred at lower MMA,
where the films are clearly aggregated, there could be some rearrangement. There is a
significant driving force for forming zirconium phosphonate linkages, and the
aggregates could rearrange during transfer to further maximize interactions with the
zirconated surface. While the porphyrins are clearly oriented parallel to the surface in
the transferred film, providing each porphyrin the chance to form multiple zirconium
phosphonate bonds, it is not known if the molecules aggregate the same way on the
water surface.
The LB procedure used in these studies takes advantage of the binding energy
of the zirconium phosphonate continuous network and is shown to be quite versatile.
Both symmetric and alternating layer films can be prepared. Use of the zirconated


6
name a few.15>22 The methods applying to the films discussed in this dissertation will
be described here.
Creep tests provide information on monolayer quality and can be recorded in
two ways. First, the monolayer is compressed to a certain pressure and then that
pressure is maintained by the barriers expanding or compressing as necessary while
recording the change in area with time. Second, the monolayer is compressed to a
defined area, which is maintained by stationary barriers, and the pressure is monitored
over time. Stable monolayers will show a static surface pressure or little movement in
the barriers after the desired pressure is reached. Unstable monolayers go through
constant and sometimes drastic rearrangements, which force contraction or expansion
of the barriers. For example, the hydrophobic nature of the amphiphile may be
insufficient and the amphiphile may dissolve into the subphase forcing the barriers to
compress to maintain n. Also, the vapor pressure of the amphiphile may lead to their
evaporation, causing the surface pressure at constant area to decrease or the barriers to
move forward to hold constant pressure in proportion to the instability of the film.
Alternatively, the amphiphiles may have a strong affinity for one another, leading to
agglomeration and either causing an anomalous change in the surface pressure at
constant area or forcing the barriers to work to maintain the surface pressure 22
Hysterisis studies monitor the effect of the monolayer stability on the
reproducibility of the isotherm upon compression and decompression. If the
amphiphiles tend to aggregate, the isotherm will not retrace its compression curve in
its decompression cycle. From creep tests and hysterisis experiments, the ability of
the monolayer to hold its form and to possibly be transferred can be ascertained.24
Reflectance UV-vis spectroscopy is used to understand the optical behavior of
monolayers of chromophore-containing amphiphiles on the water surface. One
method for studying the Langmuir monolayer by reflectance UV-vis involves placing


85
forces such as solvent, heat, or time.126 In addition, having four amphiphilic chains on
the porphyrin permits the formation of Langmuir monolayers of these materials
without diluting the amphiphiles with a good film forming amphiphile such as stearic
acid.33.88-90
The MnP4 films were first investigated on the water surface in a Langmuir
monolayer. An isotherm of this material showed significant film compressibility
(Figure 4.2). Reflectance UV-vis showed that the porphyrins formed face-to-face
dimers above ca. 10 mN m'1, which were maintained upon transfer onto glass
substrates.
The procedure for MnP4 film formation was directed by the film
characterization results. In most cases, evidence suggests that the phosphonic acid
tethers on the porphyrins were able to bind to the metal phosphonate lattice. Film
stability was monitored by UV-vis, which displayed no significant chromophore loss
after 5 minutes in hot CHC13 or CH2C12. Although the zirconium phosphonate lattice
contributes no interesting physical phenomena to the final film, the strong oxophilicity
of the phosphonate oxygens for the zirconium lattice allow for a wide variety of stable
films to be formed.
4.2 UV-vis Behavior of MnTPPs
4.2.1. Solution Studies
Both MnTPPs displayed electronic behavior in solution consistent with d-type
hyperporphyrins. Mn(II)-porphyrins have absorption spectra similar to free-base
porphyrins due to a lack of metal-porphyrin interaction; however, the absorption
spectrum of the Mn(III)-porphyrin is quite different. According to Gouterman,80
Mn(III)TPP is a classic d-type hyperporphyrin with extra absorption bands at higher


159
6.2.2. Catalysis using FL,Oo as the oxidant
6,2.2.1. Oxidation with 104 times less catalyst vs. other reactants (80 umol
FFCF or 40 pmol cyclooctene vs. 1 nmol MnP). The above-described PhlO
epoxidations were performed with lnmol of catalyst relative to 40 pmol of substrate
and 5 pmol of oxidant. The catalyst in these studies is ca. 103 times lower in
concentration than that suggested in the literature studies. The results, however,
suggest that the catalyst is still active at this concentration under these conditions.
Additionally, in the PhlO reactions, excess substrate was used to protect the catalyst
from bleaching. As mentioned in section 6.1, with peroxide oxidants, both excess
substrate and excess oxidant have been investigated.
Figure 6.7: SA ImODPA/SA MnP4 studied in the epoxidation of cyclooctene using
1122


117
at 483 nm and the blue shoulder at 463 nm was reduced in absorbance intensity. This
spectral behavior corresponds to some of the phosphonic acid ligands being displaced
by bromide. However, the bromide ligation did not appear to be quantitative, as was
the case with the MnPO. After the addition of 10 eq. of the ImODPA, the intensity of
the peak at 483 nm leveled off, and the 463 nm peak was at a minimum. With 20 or
more equivalents of ImODPA, the blue Soret peak, or Band Vi, shifted to 460 nm and
increased in intensity (Figure 5.4). This blue shift may indicate imidazole binding.
Since the ImODPA amphiphile is terminated by a phosphonic acid, it would
seem, again, that addition of this amphiphile would only serve to increase phosphonic
acid binding. The competing ligands, however, make definitive identification of the
peak at 460 nm difficult. Above a certain ImODPA concentration, it appeared that the
imidazoles were displacing the remaining phosphonic acids and possibly some
bromides and shifting Band Vi to higher energies. Therefore, a MnP(Br)(Im) species
was probably present in solution at high ImODPA concentrations. In the films of the
Mn-porphyrin, this competition may be avoided if the phosphonic acids are bound to
the zirconated ODPA template.
5.3 Film Studies
5.3.1. Langmuir-Blodgett Films containing substituted MnP4
5.3.1.1. MnP4 substituted into an HDPA LB film. To understand the ability of
the porphyrin to bind to the zirconium network in a preformed bilayer, a film was
prepared by substituting a MnP4 layer into a LB film of hexadecylphosphonic acid
(HDPA). By substituting the porphyrin film into an aliphatic capping layer, the hope
was that the phosphonic acids could secure the porphyrin to the surface while the
HDPA would be able to prevent porphyrin aggregation. The HDPA film formed in


80
Chemical modification with four alkylphosphonic acid sidegroups allows the
porphyrin to spread completely. Porphyrin PdP4 spreads to a monolayer thick film at
high MMA, and as the film is compressed, an increase in surface pressure is registered
near 200 2 molecule*1, corresponding to the area of the flat porphyrin macrocycle.
However, the side-by-side arrangement of the porphyrin chromophores is not stable as
the pressure is increased and the film rearranges, with the molecules sliding over one
another to form multiple chromophore layers. This behavior is illustrated in Figure
3.16.
Figure 3.16: Illustration of orientation and packing of PdP4 films transferred
at high and low MMA.
The films of PdP4 can be transferred at high MMA onto zirconated ODPA
templates to form monolayer or submonolayer films of the porphyrin chemisorbed to
the surface with the chromophore ring oriented parallel to the surface. Films of PdP4
can also be transferred at lower MMA, where the reflectance UV-vis indicates the


60
LB films of PdP4 and PdPl were formed incorporating a zirconium
phosphonate network. The strong tendency of zirconium ions to crosslink the
phosphonate groups precludes the normal deposition of organophosphonate
monolayers with the metal in the subphase.28 Therefore, a previously developed
three-step deposition procedure was used (Figure 2.2) as described in Chapter 2.28>38
Both symmetric (PdP/Zr/PdP) and alternating (ODPA/Zr/PdP) films have been
prepared in this way (Figure 3.2).
a b c d
Figure 3.2: Schematic of Pd-porphyrin films formed: a) alternating ODPA/Zr/PdP, b)
alternating ODPA/Zr/PdP:ODPA mixed film, c) symmetric PdP/Zr/PdP, d) symmetric
PdP: ODPA/Zr/PdP :ODP A.
Control over aggregation of the porphyrin chromophores is achieved through a
combination of molecular design and the careful choice of the conditions for transfer


5
MMA (A2 molecule'1)
Figure 1.1: Schematic of an isotherm and corresponding monolayer behavior.
1.1.1.2 Langmuir monolayer characterization: creep and hvsterisis tests and
reflectance spectroscopy. Although the isotherm is very important in identifying the
general behavior of a monolayer film, it does not give specific information about such
things as the monolayer stability, alkyl chain orientation, or aggregation of the
amphiphiles. These more specific ideas of monolayer behavior can be discerned from
experiments such as creep and hysterisis tests, reflectance UV-vis, fluorescence
microscopy, Brewster angle microscopy, and surface potential measurements,23 to


CHAPTER 3
PALLADIUM PORPHYRIN CONTAINING ZIRCONIUM PHOSPHONATE
LANGMUIR-BLODGETT FILMS
3.1. Background on Palladium Porphyrin Films
Langmuir monolayers and LB films of the derivatized palladium tetraphenyl
porphyrin molecules, palladium 5,10,15,20-tetrakis(2,3,5,6-tetrafluorophenyl-4-
octadecyloxyphosphonic acid)porphyrin and palladium 5,10,15-tris(2,6-
dichlorophenyl)-20- (2,3,5,6-tetrafluorophenyl-4-octadecyloxyphosphonic
acid)porphyrin, referred to as PdP4 and PdPl, respectively, are described in this
chapter. The central Pd metal is a four-coordinate, diamagnetic d8 metal, and is co-
planar with the porphyrin ligand. Being four-coordinate, there are no complicating
axial ligands to consider.
Porphyrins PdP4 and PdPl are substituted with four and one
octadecylphosphonic acid groups, respectively. These molecules differ from many
other porphyrin amphiphiles in that there is a hydrophilic group at the end of the alkyl
chain substituent. In many literature reports, the porphyrin group is often the
hydrophilic part of LB film forming amphiphiles.91 Molecules PdP4 and PdPl
(Figure 3.1) were designed to investigate whether porphyrins can be incorporated into
metal phosphonate LB films. Also, because of their well-understood spectroscopic
behavior, the PdP molecules were used to study how the orientation and aggregation
of the porphyrin can be controlled in the deposited films.
58


26
The Q-Bands are observed between 500 and 600 nm. The lower energy Q-
Band (Qa) is associated with the electronic origin, Q(0,0) of the lower energy singlet
excited state. The higher energy Q-Band (Qp) has a contribution from a vibration
mode and is denoted Q(1,0). Both Q(0,0) and Q(1,0) are quasi-allowed transitions
with relatively low absorbance intentisties. The Q-Bands are highly sensitive to the
symmetry of the molecule. In porphyrins of D4h symmetry such as metalloporphyrins,
or the diacidic or dibasic forms of the porphyrin, two Q Bands are observed as
pictured in Figure 1.12. The free-base porphyrin is of D2h symmetry and the
degeneracy of the Q-Bands is disrupted, splitting the Q-Bands into four peaks.80
The above described transitions are due to the porphyrin ^-electrons and are
n-n* in nature. If these transitions are unperturbed by the central substituent, the
Figure 1.13: Outline of 16-member principal resonance structure of metallo-
porphyrin.
porphyrin is classified as "regular". Similarly, the emission spectra of regular
porphyrins are determined solely by the chromophore itself. The above explanation of
the UV-visible behavior of porphyrins is based on the free-electron model, in which
the core of the porphyrin, the 16-member heterocyclic, conjugated ring behaves like a
free-electron wire (Figure 1.13). Another popular theory is Gouterman's four-orbital


147
dichlorobenzene standard was used in the H202 reactions. The sensitivity factors were
calculated using Equation 2.2:
WCyOO^S
xCyOO
wsA>
yOO
(2.2)
and were found to be 1.297 for cyclooctene oxide (CyOO) and 1.008 for cyclooctene
(CyCO) with decane. After average k values were obtained for the CyO and CyOO,
the catalysis yields were determined from a GC of the reaction mixture using Equation
2.3. The amount of product was calculated in grams, and referenced to the theoretical
mass to obtain a percent yield. An empirical sensitivity factor for each compound is
necessary due to the fact that the GC detector does not respond identically to each
solute.
WCyOO -
\yOO
yOO
4,
6.2 Results
(2.3)
6.2,1 Catalysis with PhIO as the oxidant
6.2.1.1. Time dependence of oxidation yields. A stock solution of CyO and
PhIO with decane was prepared in CH2C12 solution at a 1000:125:500 molar ratio in
CH2C12. A 1 mL aliquot contained 40 pmol CyO, 5 pmol PhIO and 20 pmol of
decane, which was then used for the blank reactions with no porphyrin present.
Considering the amount of porphyrin in the films to be approximately 1 x 10'9 moles,
the molar ratio of the corresponding homogeneous reaction was .001:40:5:20 in, again,
1 mL of CH2C12. Also, ca. 1 mL of the stock solution was introduced into the flow


110
ImODPA are anticipated to be located below the chromophore plane; however, only
one has the opportunity to bind at a time to the metallo-porphyrin core.
Figure 5.1: Structures of A) MnP4, B) MnPO, C) ImODPA and D) ImH.


65
interaction of the chromophores at different pressures. At MMA larger than and
comparable to the size of the chromophore itself, the porphyrin rings cannot be
aggregating to any significant extent or the onset of surface pressure would occur at
lower areas. The red shift of the Soret Band as the area is decreased indicates
enhanced chromophore aggregation at lower MMA.
Figure 3.6: Reflectance UV-vis of PdP4 on water subphase.
In contrast to PdP4, the IT-A isotherm of PdPl (Figure 3.7) indicates that these
molecules aggregate even in the absence of applied pressure. No significant increase
in surface pressure is seen until areas below 120 2 molecule-1. The pressure rises to
only 5 mN m-1 at 60 2 molecule-1, below which the pressure increases until the film
collapses below 36 2 molecule-1. The isotherm cannot reflect a true molecular
monolayer, but rather results from the compression of aggregates at the water surface.


51
butanol in CDC13 was injected into a small capillary tube using a long syringe needle.
The depth of the solution in the capillary tube reached approximately 2. Two
standard NMR tubes were then filled to approximately 1 with sample solution. The
first was filled with pure MnPO (0.0106 g, 100 pmol) dissolved in the 10% t-
butanol/CDCl3 solution. The second was filled with MnPO (0.0106 g, 100 pmol) and
ethylphosphonic acid (0.220 g, 2000 pmol). The reference solution in the capillary
was inserted into the porphyrin containing NMR sample, and the magnetic
susceptibility of the solute, xg (cm3 g'1) induced by the magnetic porphyrin was
approximated by:
v --3A/
g A7ufm
(2.1)
where Af is the diamagnetic frequency shift, f is the spectrometer frequency, and m is
the mass of substance per mL of solution. Compared to literature values, the
differences in the xg of MnPO with and without ethylphosphonic acid did not
correspond to a spin state change in the Mn(III).
2,2.3. Manganese Porphvrin/Imidazole Mixed Films
The general method used to prepare MnP4/imidazole films in this study
involved the initial formation of a zirconated octadecylphosphonic acid (ODPA)
template, as before. Onto this template, a film of either pure imidazole
octadecylphosphonic acid (ImODPA), which was prepared by the Bujoli group, or a
mixture of ImODPA and MnP4 could be formed. The zirconium phosphonate
network provided a means for locking the porphyrin and the imidazole into the films,
resulting in films that were stable toward the conditions used for the catalysis


20
subsequently metallated, and the cycle continued until multilayered films were
fabricated.
The self-assembly of metal phosphonate films is made possible by a very
strong attraction between certain metal ions, particularly the tetravalent metals such as
Zr4+, for the phosphonate groups of alkyl phosphonic acids.6163 However, the
individual metal salts and the phosphonate are themselves soluble. This particular
affinity between metal and phosphonate, makes possible the formation of
monomolecular layers during each step of the cycle and the ability to assemble
controlled multilayers.
1.2.3. Metal Phosphonate Langmuir-Blodgett Films
Two methods of film formation have been employed to incorporate the metal
phosphonate lattice into the polar region of LB films, one for the divalent and trivalent
metals which are soluble in acidic media, and one for the tetravalent and some
trivalent metals which are insoluble even at low pH. A schematic comparing
traditional LB films to metal-phosphonate LB films is shown in Figure 1.9.
uuC
TTTTT
A
Hydrophobic
region
Polar
region
*
Metal
phosphonate
region
Figure 1.9: Comparison between A) traditional LB films and B) metal-phosphonate
LB films.


170
(116) Battioni, P., Renaud, J.P., Bartoli, J.F., Reina-Artiles, M., Fort, M., Mansuy, D.
J Am. Chem.Soc 1988,110, 8462-8470.
(117) Kern, W. J. Electrochem. Soc. 1990,137, 1887-1892.
(118) Advincula, R. Dissertation, University of Florida, 1994.
(119) Evans, D. F. J. Chem. Soc. 1950, 2003.
(120) Schubert, E. M. J. Chem. Ed. 1992, 69, 62.
(121) Saltzman, H., Sharefkin, J.G. Organic Synthesis 43, 60-61.
(122) Lucas, H. J., Kennedy, E.R. Organic Synthesis Coll. Vol. 3, 483, 1955.
(123) Montanari, F. Metalloporphyrins Catalysed Oxidations-, Kluwer Academic
Publishers, 1994.
(124) Caughey, W.; Deal, R.; Weiss, C.; Goutermann, M. J. Mol. Spec. 1965,16,
451-463.
(125) Talham, D. R.; Seip, C. T.; Whipps, S.; Fanucci, G. E.; Petruska, M. A.; Byrd,
H. Comments Inorg. Chem. 1997,19, 133-151.
(126) Petruska, M. A., Talham, D.R. Langmuir 2000, submitted.
(127) Day, V. W., Stubs, B.R., Tasset, E.L., Day, R.O., Marianelli, R.S. J. Am.
Chem. Soc. 1974, 96, 2650-2652.
(128) Tulinsky, A., Chen, B.M.L. J. Am. Chem. Soc. 1977, 99, 3647-3651.
(129) Hansen, A. P., Goff, H.M. Inorg. Chem. 1984, 23, 4519-4525.
(130) Schardt, B. C., Hollander, F.J., Hill, C.L. J. Am. Chem. Soc. 1982,104, 3964-
3972.
(131) Boucher, L. J. J Am. Chem. Soc. 1970, 92, 2725-2730.
(132) Powell, M. F., Pai, E.F., Bruice, T.C. J. Am. Chem. Soc. 1984,106, 3277-3285.
(133) Mu, X. H., Schultz, F.A. Inorg. Chem. 1992, 31, 3351-3357.
(134) Maiti, N. C., Mazumdar, S., Periasamy, N. J. Phys. Chem. B 1998,102, 1528-
1538.
(135) Nixon, C. M.; Claire, K. L.; Odobel, F.; Bujoli, B.; Talham, D. R. Chem.
Mater. 1999,11, 965-976.


82
ODPA template layer allows almost any phosphonic acid derivatized amphiphile to
transfer in a capping layer.28-3865125 Unlike conventional LB depositions, films of
PdP4 and PdPl can be transferred onto the zirconated template layers at any surface
pressure, allowing, in the case of PdP4, the arrangement of the molecules in the
transferred films to be tuned by choice of the area-per-molecule at deposition. The
films do not need to be stable Langmuir monolayers in order to transfer, as the driving
force is formation of the zirconium phosphonate bonds. It is the strength of the
zirconium phosphonate interaction, in particular the lattice energy associated with the
zirconium phosphonate extended network, that is responsible for the exceptional
stability of these non-traditional LB films.28-38
Zirconium phosphonate LB films, like solid-state zirconium phosphonates, are
insoluble in organic solvents and under most aqueous conditions. The inorganic
network has also been shown to enhance the thermal stability of LB films.126 The
zirconium phosphonate inorganic extended network adds substantial stability to the
films, which are insoluble under most organic and aqueous conditions. The methods
developed here with the palladium tetraphenyl porphyrins can also be applied to other
porphyrin systems, and in this way the vast array of physical and chemical
characteristics of porphyrins, including catalytic activity, should be able to be
incorporated in stable LB films.


63
the excited states in 7t-7t* transitions, shifting this Band to lower energies.25-26 As the
concentrations of both PdP4 and PdPl were raised, the Soret Band systematically
shifted blue to 407 and 411 nm for the porphyrins PdP4 and PdPl, respectively,
implying H-aggregation of the chromophores in EtOH.76-92 Going from EtOH to
CHC13 to H20, at 10"6 M, there is an obvious red shift in the Xmax. This red shift does
not correspond to a solvent polarity shift, but it does correspond to a shift in the
solubility of PdP4. PdP4 is very soluble in EtOH and only slightly soluble in water.
Figure 3.4 Solution UV-vis of PdP4 in EtOH and water compared to CHC13.
3.2,2 Langmuir Monolayers of Palladium Porphyrins
The room temperature pressure (11) vs. area (MMA) isotherm of PdP4 on water
at pH 5.5 is shown in Figure 3.5. There is a measurable onset of surface pressure near
220 2 molecule'1, followed by a gradual increase in pressure as the film is
compressed, with an apparent phase transition giving a steeper rise in pressure near


41
The heterocyclic imidazole ligand has been shown to improve the catalytic
efficiency of Mn-porphyrins, and MnP4 films containing the imidazole ligand have
been successfully developed. These films were prepared by a variety of methods
involving a combination of LB, SA and substitution procedures. In solution, it is seen
that binding of a non-amphiphilic imidazole causes a small blue shift of the Mn-
porphyrin Soret band; however, a dominant influence on the Soret band in the films
and in solutions containing the ImODPA ligand comes from the metals axial
environment -- especially halide binding. Mixed films containing both the imidazole
phosphonic acid (ImODPA) and the MnP4 molecules have been prepared and
characterized by ATR-IR, UV-vis, and XPS. The preparation and characterization of
imidazole and MnP4 containing films is presented in Chapter 5.
The epoxidation of cyclooctene using iodosylbenzene was catalyzed by the
pure MnP4 containing films with substrate to oxidant ratios of 20:5, 40:5, and 60:5
over a variety of reaction times. The self-assembled MnP4 films proved to have
slightly improved catalytic efficiency relative to the analogous LB films likely due to
the increased aggregation observed in LB deposited films. The mixed
ImODPA/MnP4 films showed catalytic activity in the presence of the peroxide
oxidants. These films were examined with different substrate to oxidant ratios. The
porphyrin containing films, both with and without ImODPA were resistant to
degradation under most examined reaction conditions. The catalysis results involving
both PhIO and H202 oxidants with pure porphyrin and mixed porphyrin/imidazole
films are described in Chapter 6.


30
In addition to intramolecular effects such as the metal, substituents, and axial
ligands, intermolecular effects such as aggregation can significantly alter the electronic
behavior of porphyrins. Aggregation in these chromophores has been described
thoroughly by Kasha's exciton theory. This theory looks at aggregation only from the
point of view of overlapping transition dipole moments (Figure 1.15) and not as
interacting 7r-systems. In metallo-porphyrins, the transition dipole moments are
equivalent due to the symmetry of the chromophore.76-8283

My
Figure 1.15: Transition dipole moments in metallo-porphyrin.
Aggregation, according to Kashas model, splits the excitation energy of the
monomer (E) into high and low energy components. Equation 1.8 describes the
energy dependence on aggregation by:
E = E + DV
(1.8)
where D is the dispersion energy which is highly dependent on the change in
environment upon aggregation, and V is the exciton splitting energy. 76,83,84


140
physisorption of a number of chromophores is expected due to the propensity of the
porphyrins to aggregate. However, this implies a significant reorganization of the
underlying imidazole monolayer in order to have room to incorporate these alkyl
chains.
After 30 min in hot CHC13, the absorbance intensity leveled off at 0.011 au and
va(CH2) peak occurred at 2928 cm-1, as referenced to the imidazole monolayer (Figure
5.22A). This result indicates that the true porphyrin containing monolayer contains
alkyl chains that are disorganized and include a number of gauche interactions. After
removing the physisorbed chromophores, the true MnP4 monolayer characteristics
were better defined.
Also, the SA of this film for only 5 min, leading to an absorption intensity of
0.004 au, formed a SA film containing approximately 30% of a complete imidazole
monolayer. This incomplete film was then exposed to a MnP4 solution. After 30 min,
the absorbance intensity leveled off at 0.018 au and the va(CH2) was at 2926 cm-1.
After only 10 min in hot CHC13, the absorbance dropped drastically to 0.005 au and
va(CH2) shifted to 2937 cm-1 (as referenced to the imidazole monolayer). However,
the IR shows that the SA of a 30% ImODPA layer resulted in a relatively poor
monolayer, which left many defect sites. Originally, it was thought that these defect
sites would allow for the more straightforward inclusion of the porphyrin.
Unfortunately, the imidazole layer in such a state may be easily removed from the
zirconated ODPA template, and the final film may include less imidazole and
porphyrin (Figure 5.16B), and therefore, have a lower overall alkyl absorbance in the
IR.


97
90 orientation relative to the surface normal. When transferred after the plateau
region, at areas much smaller than the chromophore itself, the tilt angles were
consistently ca. 90, further confirming the presence of stacked rather than tilted
chromophores.
The stability of films transferred by the LB technique before, during, and after
the plateau region of the isotherm were tested by exposing the films to hot CHC13 for
up to 60 min each. When transferred at 15 mN m'1 (Figure 4.10A), the original Soret
Band was at 455 nm. After rinsing, the Band Vi shifted to 463 nm and a second Soret
Band appeared at 477 nm. This red shift in the band associated with phosphonate
binding is probably due to elimination of H-aggregated, physisorbed chromophores.
Band Vi observed before and after rinsing in the films transferred at high MMA,
remained at the same energy indicating that there was no significant change in the
chromophore interaction at this transfer area. Because chromophore interaction was
expected to be low at this MMA before rinsing, it was not surprising that no shift was
observed. In each case, the absorbance intensity decreased significantly during the
first five minutes of solvent exposure, and then leveled off (Figure 4.10). The
formation of two Soret Bands, Vi and Vii, makes it difficult, however, to truly assign
the change in absorbance intensities to a removal of chromophores.
The phosphonic acids in the MnP4 would probably have a stronger tendency to
be on the water surface than bound to the porphyrin. Considering the strong tendency
for the Mn-porphyrins to bind water in the axial positions, the chromophore could be
very hydrophilic, promoting their tendency to lay on the water surface. This behavior
was observed in MnP4 films transferred at high MMA. In films transferred at lower
MMA, chromophore aggregation may have kept many phosphonates from binding to
the zirconium network, leaving them available for binding the manganese. Therefore,


35
vV
O
concerted
oxene insertion
/=\
possible rate-limiting
formation of a charge-
transfer complex
Figure 1.17: Suggested mechanism of olefin epoxidation catalyzed by MnTPP.
1.3.3. Immobilization of Porphyrins
The ability of porphyrins to efficiently catalyze both the epoxidation of olefins
and the hydroxylation of alkanes unfortunately leaves the porphyrin and its
superstructure vulnerable as potential substrates. However, nature has developed
mechanisms to eliminate these unwanted complications. For example, an enzyme and
its cofactors may form metal-oxo complexes only when the substrate molecule is
confined within an enzymatic cavity. Also, the tertiary protein structure prevents the
active porphyrin catalyst from approaching other potentially oxidizable
metalloporphyrins, and it makes the structure rigid, protecting the amino acid
backbone and the side-chains from intermolecular oxidation by contacting the active
site. These biosystems are difficult to mimic in the laboratory; however, successful


126
Figure 5.10: MnP4 substituted onto a pure ImODPA SA film.
5.3.2.2. Reversibility of the chloride binding in MnP4 substituted films. The
same reversibility of the halide binding was observed in the films of MnP4 substituted
into SA ImODPA films. As shown in Figure 5.11, after 24 hr, the peak at 477 nm
reduced in intensity while the peak at 460 nm increased in intensity. The halide
binding could be achieved again by rewetting this film, and the cycle continued for up
to a week. However, with each cycle, the halide binding became slightly more
persistent. The reversibility of the binding, as observed by the shifts in the Soret
Bands, indicated that the molecular behavior in these ultrathin films was not static. In
fact, in thin films, the porphyrins were keenly sensitive to the environment, especially
environments containing potential axial ligands.


CHAPTER 6
MANGANESE PORPHYRIN AND IMIDAZOLE CONTAINING
ZIRCONIUM PHOSPHONATE THIN FILMS AS CATALYSTS
6.1 Background
Reactions using immobilized catalysts have recently gained much interest. First, the
immobilized porphyrins are somewhat protected from destructive oxidation because they
are ideally isolated from one another on the surface. Elimination of destructive oxidation
can improve the catalysts turnover rates and overall reaction yields. Secondly, when the
catalyst is immobilized, its recovery is trivial. Therefore, if the catalyst is still active, the
film can be recycled and used in another catalytic reaction. With these motivations,
reactions using the MnP4 films, either pure or with ImODPA, were studied. Along with
the overall reaction yield, the optical intensities of the porphyrin films before and after
the reaction were monitored to determine if the porphyrins were bleached or removed
from the surface during the course of the reaction.
Battioni et al. examined the epoxidation of olefins using hydrogen peroxide as the
oxidant.116 In this report, Battioni investigated conditions using 5,10,15,20-tetrakis(2,6-
dichlorophenyl)porphyrin (MnTDCPP(Cl)) and 5,10,15,20-
tetrakis(pentafluorophenyl)porphyrin (MnTFPP(Cl)) with both A) excess substrate and
B) excess oxidant. The molar ratio in condition Awith MnTDCPP(Cl) was 800:10:20:1,
cyclohexene to imidazole to H2O2 to catalyst, and under these conditions, reported
cyclohexene oxide yields of 97% were observed. The molar ratio
144


5.3.5 Characterization of films containing MnP4 and ImODPA
by XPS and ATR-IR 134
5.4 Conclusions 141
6 MANGANESE PORPHYRIN AND IMIDAZOLE CONTAINING
ZIRCONIUM PHOSPHONATE THIN FILMS AS CATALYSTS 144
6.1 Background 144
6.2 Results 147
6.2.1 Catalysis With PhIO as the Oxidant 147
6.2.2 Catalysis Using H2O2 as the Oxidant 159
6.3 Conclusions 163
REFERENCES 164
BIOGRAPHICAL SKETCH 171
vi


49
pressure and low pressure transfers, respectively. The transfer ratios of the porphyrin
films mixed with ODPA consistently showed uncorrected transfer ratios near unity.
Monolayers of PdP 1 and PdP4 were also studied on both heated and basic
subphases. To heat the trough, an Isotemp Refrigerating Circulating Model 900
(Fisher Scientific) pump with a water/ethylene glycol bath was used. The temperature
of the subphase was monitored using a KSV thermosensor. A 0.01 M KOH solution
was added to the subphase to adjust the pH to the desired value.
PdP4 films were also studied by self-assembly. The SA solution was prepared
by diluting 1 mL of a 0.5 mg mL'1 solution of PdP4 in CHC13 to 30 mL with a 9/1
EtOH/H20 mixture. The film was allowed to SA for approximately 2 hours before
studying by UV-vis.
2.2.2. Manganese Porphyrin Films
Manganese 5,10,15,20-tetrakis(2,3,5,6-tetrafluorophenyl-4-
octadecyloxyphosphonic acid)porphyrin (MnP4) and a model porphyrin, manganese
5,10,15,20-tetrakis (pentafluorophenyl)porphyrin (MnPO) were prepared by the Bujoli
group. Again, ODPA was used for the template layers, zirconyl chloride was used to
prepare the zirconium network, and CHC13 was used as the spreading solvent. Also, t-
butylammonium chloride (i-BuNH2+ Cl') (Aldrich) was used as a chloride source for
SA deposited films. NaCl (Acros) was used as the chloride source for LB transferred
films.
To form the MnP4 monolayers, a 0.4 mg mL'1 solution was prepared in CHC13
(often, in order to dissolve the porphyrins, up to 5% ethanol was added and the
solution was sonicated for about an hour). An appropriate volume of solution was
spread on the aqueous surface in order to reach and hold the desired transfer pressure


143
From solvent studies, it is clear that the imidazole can displace either
phosphonic acid or chloride ligands if present in a high enough concentration. This
binding is in equilibrium, making this again, difficult to consistently observe in the
UV-vis. However, it is believed that in the case of the catalysis reaction, the binding
will be favored due to the excess of imidazole present and that this binding will cause
the activation of the porphyrin for catalysis using peroxide oxidants even if it is not
consistently observed by UV-vis.


101
However, this five-coordinate structure was not rigid. When the films were
left to structurally relax overnight, the peak at 477 nm decreased in intensity and the
blue shoulder became more intense. This reversible behavior indicates that the ligand
environment, which is very sensitive to solvent and heat, is flexible (Figure 4.13).
Figure 4.13: MnP4 self-assembled from EtOH/H20 and rinsed in CHC13. The legend
indicates the spectra after rinsing, after being left overnight and the rinsed again over a
three day period.
When these films were rinsed in CH3CN, behavior similar to CHC13 rinsing
was observed. The band at 477 nm, again, increased and the band at 464 nm
decreased in intensity with time in the hot solvent. Again, if the film was left
overnight, the band intensities reversed (Figure 4.14). Hot CH3CN, therefore, also
eliminated the phosphonic acid ligand and caused the formation of the five-coordinate
MnTPP(Cl). When the film relaxed, the phosphonic acids had a tendency to bind
again to the central metal forming the six-coordinate MnTPP(Cl)(PA) structure.


2
films.16 His associate, Katherine Blodgett first transferred these films from the water
surface onto solid supports.17
The SA technique was first described in scientific reports in the late 1940s and
mid 1950's.1819 This technique relies on surface-active molecules and the appropriate
surface being placed in contact with one another through a solvent medium. The films
prepared by this method tend to be more stable than traditional LB films because of
the types of surface interactions that drive their formation.
The traditional LB technique employs different surface interactions depending
on the method of transfer. First, as in the case of hydrophilic-hydrophilic transfers of
neutral amphiphiles from a pure aqueous subphase, the interactions are primarily
hydrogen bonding in nature. Ionic bonding is commonly observed in the case of
hydrophilic-hydrophilic transfers from a metal ion-containing subphase. In the case of
hydrophobic-hydrophobic transfers, van der Waals interactions are involved. During
LB depositions, the film is usually physisorbed to the surface implying some through-
space interaction, while in SA films, the molecules are adsorbed to the surface through
a chemical bond. The SA method relies on the formation of covalent bonds between
the surface-active component of the molecule and the solid substrate often resulting in
more stable films.20
In LB films, the hydrophilic head group typically dictates the area the molecule
fills in the interfacial region. The alkyl groups, therefore, adjust to maximize the van
der Waals contacts leading to organized packing within this region.21 Unfortunately,
control over the film packing and organization achieved by the LB technique is absent
in the SA method. The molecular organization in SAMs (self-assembled monolayers)
is dictated solely by the geometry of the active sites on the surface. However, in LB
films, the pressure and area of deposition can be selected to deposit a particular phase
of the monolayer and to influence the transferred film organization. An understanding


13
Using polarizers and stages that allow careful placement of the substrates at different
angles of incidence to the beam, the orientation of the chromophores within the films
can be determined. By comparing the absorbance intensity in the s- and p-
polarization, a dichroic ratio can be calculated using Equation 1.6:
D=j- 0.6)
P
Orientational order within the plane of the film and substrate is obtained by looking at
results from 0 and 900 (s and p) polarization as the beam is normal to the surface (0
angle of incidence). Studying the polarization at higher angles of incidence (typically
45) enables the determination of the orientation out of the plane (Figure 1.6).
0 polarization
Figure 1.6: Schematic of polarized UV-vis experimental beam directions.


38
1.3.4.2. Spectral evidence of axial ligand. ImH to porphyrin binding should be
apparent in the UV-vis spectra. The formation of a bis-imidazole Mn(III)TPP Cl
complex was demonstrated by a broadening shift in the Soret Band from 478 nm for
the pure porphyrin to 472 nm.111 Interestingly, the equilibrium constants for the
formation of the mono- and bis-ligated imidazole-porphyrin complexes are similar and
their absorption spectra are nearly identical. Therefore, at high concentrations of
imidazole in solution, it is possible that the observed spectra arise from the formation
of bis-imidazole complexes.11 *413 However, the preferred formation of the mono- vs.
bis-imidazole complexes has caused some disagreement, and some authors claim that
even at saturated concentrations of imidazole, the principal component is the mono
imidazole only.114
In the UV-vis of the Mn-porphyrin, the Soret Band of the Mn-porphyrins is the
most sensitive to the axial ligand. The change in the Soret energy is due to the charge
induced on the porphyrin chromophore through the metal. Electron-donating axial
ligands induce negative charge on the macrocycle, separating the bonding and anti
bonding orbitals of the porphyrin, and increasing the transition energy.115 Hard
anions, whose binding is strengthened by increased ionic character of the central
metal, prefer localization of positive charge on the metal, which leaves the
chromophore with more negative charge.115 Similarly, as a basic ligand takes on more
hard base character, the will shift to higher energies.
1.4 Dissertation Overview
The overall goal of this dissertation was to prepare zirconium phosphonate thin
films by both the SA and LB technique that contained catalytic Mn-porphyrins. The
purposes of the zirconium phosphonate network were to stablize the manganese


114
of the imidazole was added, an obvious blue shift of about 20 nm to ca. 458 nm was
observed in the Xmax (Figure 5.3A).
350 400 450 500 550 600
Wavelength (nm)
Figure 5.3: Solvent response of A) MnPO and B) MnP4 to ImH.
Upon addition of ImH to MnP4 solutions in CH2C12, the original red shoulder
on the Soret Band disappeared and was followed by a blue shift of the A.max to 458 nm


36
biomimetic catalysts have been prepared with bulky, rigid groups substituted on the
porphyrin chromophore.101
One alternative solution to the problem of internal oxidation or intermolecular
oxidative destruction of the porphyrin catalyst is immobilization of the chromophore.
Immobilization involves tethering the porphyrin to a surface such as a film,88 an
inorganic solid particle,103'106 a polymer,107-108 a membrane,109 or a resin.110
Immobilized porphyrins as biomimetics and as heterogeneous catalysts have been well
explored in the past several years.104'106110 Tethering of porphyrins to a solid support
can not only reduce or eliminate oxidative destruction of the active catalyst, but can
also aid in the catalyst recovery after the reaction is completed.
Heterocyclic ligands are commonly used as the link between the porphyrin and
surface in many immobilized porphyrin systems.9498111 Unfortunately, binding the
metallo-porphyrin to the imidazole allows little control over the porphyrin orientation
in the films. Additionally, in these circumstances, there is no chemical connection
between the porphyrin and the surface other than the ligand, which leaves the
porphyrin vulnerable to removal from the surface by ligand displacement, changing
the reaction conditions.3094-98111 An alternative method for tethering the porphyrins
to surfaces has been established, which uses four alkyl phosphonic acid substituents
that can be attached to a zirconium phosphonate network making a very stable
catalytic film.
1.3.4 Heterocyclic Ligand Cocatalvsts
1.3.4.1, Ligand activation of the porphyrin catalyst. Heterocyclic ligands are
well documented in the literature as activating Fe(III) and Mn(III) porphyrins for
catalysis with oxidants such as alkyl or hydrogen peroxides.949899 Porphyrins


77
Table 3.2: UV-vis data from symmetric and alternating films of PdPl. Xmzx is given
for monolayers, and interlayer thickness is given for multilayers of films transferred
under a variety of transfer conditions.
Film
Area of
Transfer
(Vmolecule)*
riof
Transfer
(mN/m)
Temp
(C)
(nm)
thickness
()
OPA/Zr/PdPl
73
4
23-25
426
OPA/Zr/PdP 1
52
12
23-25
426
61
OPA/Zr/ PdPl
41
25
23-25
428

OPA/Zr/ PdPl
38
30
23-25
428

OPA/Zr/ PdPl
36
35
23-25
428

OPA/Zr/10%
27
12
23-25
426
48
PdPl
OPA/Zr/25%
30
12
23-25
426

PdPl
OPA/Zr/50%
38
12
23-25
426

PdPl
OPA/Zr/PdPl
300

23-25
416
OPA/Zr/ PdPl
190
4
23-25
416

OPA/Zr/ PdPl
300

23-25
414

OPA/Zr/PdPl
73
4
40
424

OPA/Zr/10%
30
12
40
424
PdPl
OPA/Zr/10%
26
20
40
425

PdPl
OPA/Zr/25%
30
12
40
424
PdPl
PdPl/Zr/ PdPl
52
12
23-25
426

10% PdPl/Zr/
26
20
23-25
426
48
10% PdPl
* Area of the chromophore and diluent as determined from Figure 3.7 (isotherms)
** Corresponding pressure from Figure 3.7 (isotherm)
*** pH of nano-pure water from filtration system is about 5.5


23
higher onset and shallower incline. We believe this isotherm behavior is due to the
rigid films causing deflections in the Wilhelmy balance rather than showing an
increase in surface pressure.
1.2.4. Dual-Function Langmuir-Blodeett Films
After the extensive characterization of simple alkyl metal phosphonate LB
films, there was interest in incorporating function into the organic region that might be
paired with properties in the inorganic lattice to form a "dual function" LB film. As
models, phenoxy and biphenoxy alkyl phosphonic acids were prepared, and divalent,
trivalent, and tetravalent metal phosphonate films were studied. 65>66 Additionally,
films containing azobenzene-derivatized phosphonic acid amphiphiles were
synthesized, and metal phosphonate films were formed also with divalent, trivalent,
and tetravalent metals.67 These results prove that larger organic groups can be
incorporated into the metal phosphonate LB films while maintaining the integrity of
the inorganic lattice structure.
Potential applications of dual functional metal-phosphonate thin films include
magnetic switches, in which the magnetic behavior of the inorganic lattice can be
altered by a structural change in the organic region. Also, films containing a
conductive or non-linear optic organic region as well as a magnetic inorganic lattice
could act as a sensor. This dissertation will focus on the preparation of porphyrin
containing zirconium phosphonate films where the metal phosphonate lattice acts to
stabilize the films toward potential catalytic reaction conditions.



PAGE 1

0(7$//23253+<5,1 &217$,1,1* =,5&21,80 3+263+21$7( 7+,1 ),/06 6758&785( $1' &$7$/<6,6 %\ &+5,67,1( 0$5,( 1,;21 /(( $ ',66(57$7,21 35(6(17(' 72 7+( *5$'8$7( 6&+22/ 2) 7+( 81,9(56,7< 2) )/25,'$ ,1 3$57,$/ )8/),//0(17 2) 7+( 5(48,5(0(176 )25 7+( '(*5(( 2) '2&725 2) 3+,/2623+< 81,9(56,7< 2) )/25,'$

PAGE 2

$&.12:/('*0(176 )LUVW ZRXOG OLNH WR WKDQN VRPH RI WKH WHDFKHUV ZKR KDYH SRLQWHG PH WRZDUG FKHPLVWU\ DQG VXSSRUWHG PH LQ WKLV ORQJ HGXFDWLRQDO DGYHQWXUH WKDQN 0U 5RJHU &UDLJ IURP /H[LQJWRQ +LJK 6FKRRO IRU EHLQJ VR H[FLWHG DERXW FKHPLVWU\ DQG 'U -LP 0F&DUJDU IRU EHLQJ D WLUHOHVV DPEDVVDGRU RI JHQHUDO DQG SK\VLFDO FKHPLVWU\ DQG IRU HQFRXUDJLQJ SXVKLQJ"f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

PAGE 3

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f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

PAGE 4

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

PAGE 5

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

PAGE 6

&KDUDFWHUL]DWLRQ RI ILOPV FRQWDLQLQJ 0Q3 DQG ,P2'3$ E\ ;36 DQG $75,5 &RQFOXVLRQV 0$1*$1(6( 3253+<5,1 $1' ,0,'$=2/( &217$,1,1* =,5&21,80 3+263+21$7( 7+,1 ),/06 $6 &$7$/<676 %DFNJURXQG 5HVXOWV &DWDO\VLV :LWK 3K,2 DV WKH 2[LGDQW &DWDO\VLV 8VLQJ +2 DV WKH 2[LGDQW &RQFOXVLRQV 5()(5(1&(6 %,2*5$3+,&$/ 6.(7&+ YL

PAGE 7

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

PAGE 8

/,67 2) ),*85(6 )LJXUH SDJH 6FKHPDWLF RI DQ LVRWKHUP DQG FRUUHVSRQGLQJ PRQROD\HU EHKDYLRU 6FKHPDWLF RI ; < DQG =W\SH /DQJPXLU%ORGJHWW PXOWLOD\HUV ;UD\ GLIIUDFWLRQ GLDJUDP ,OOXVWUDWLRQ RI $75,5 ([SHULPHQW 6FKHPDWLF RI ;36 H[SHULPHQW 6FKHPDWLF RI SRODUL]HG 89YLV H[SHULPHQWDO EHDP GLUHFWLRQV %HKDYLRU RI WKH REOLTXH GLFKURLF UDWLR YHUVXV DQ RULHQWDWLRQ SDUDPHWHU 3f &U\VWDO VWUXFWXUH RI ]LUFRQLXP SKRVSKDWH &RPSDULVRQ EHWZHHQ WUDGLWLRQ /% ILOPV DQG PHWDOSKRVSKRQDWH /% ILOPV 6FKHPDWLF RI IRUPDWLRQ RI GLYDOHQW RU WULYDOHQW PHWDO SKRVSKRQDWH ILOPV 6WUXFWXUHV RI SRUSK\ULQW\SH PROHFXOHV $f SRUSKLQH %f IUHH EDVH SRUSK\ULQ DQG &f SWKDORF\DQLQH 89YLV VSHFWUXP RI D PHWDOORSRUSK\ULQ 3G733f 2XWOLQH RI PHPEHU SULQFLSOH UHVRQDQFH VWUXFWXUH RI PHWDOORSRUSK\ULQ *RXWHUPDQfV IRXURUELWDO PRGHO 7UDQVLWLRQ GLSROH PRPHQWV LQ PHWDOORSRUSK\ULQ 3RUSK\ULQ FKURPRSKRUH LQWHUDFWLRQV 7KH VTXDUH UHSUHVHQWV WKH FKURPRSKRUH DQG LWV GLVHFWLQJ D[HV $f +W\SH RU IDFHWRIDFH DJJUHJDWHV %f HGJHWRHGJH DJJUHJDWHV &f -W\SH RU KHDGWRWDLO DJJUHJDWHV 6XJJHVWHG PHFKDQLVP RI ROHILQ HSR[LGDWLRQ FDWDO\]HG E\ 0Q733 9OOO

PAGE 9

6FKHPDWLF RI /DQJPXLU%ORGJHWW WURXJK DQG PRQROD\HU 6FKHPDWLF RI WKH WKUHHVWHS GHSRVLWLRQ SURFHVV XVHG IRU ]LUFRQLXP SKRVSKRQDWH ILOPV 6FKHPDWLF RI FDWDO\VLV FHOO VLGH YLHZ 6FKHPDWLF RI FDWDO\VLV FHOO WRS YLHZ 6WUXFWXUHV RI $f 3G3 DQG %f 3G3O 6FKHPDWLF RI 3GSRUSK\ULQ ILOPV IRUPHG Df DOWHUQDWLQJ 2'3$=U3G3 Ef DOWHUQDWLQJ 2'3$=U3G32'3$ PL[HG ILOP Ff V\PPHWULF 3G3=U3G3 Gf V\PPHWULF 3G32'3$=U3G32'3$ 6ROXWLRQ 89YLV RI 3GSRUSK\ULQV LQ &+& $f 3G3 %f 3G3 6ROXWLRQ 89YLV RI 3G3 LQ (W2+ DQG ZDWHU FRPSDUHG WR &+&, ,VRWKHUPV RI 3G3 SXUH DQG PL[HG ZLWK 2'3$ 3G32'3$f RQ D ZDWHU VXESKDVH 5HIOHFWDQFH 89YLV RI 3G3 RQ ZDWHU VXESKDVH ,VRWKHUPV RI 3G3O SXUH DQG PL[HG ZLWK 2'3$ 3G3O 2'3$f RQ D ZDWHU VXESKDVH 5HIOHFWDQFH 89YLV RI 3G3O RQ ZDWHU VXESKDVH 5HIOHFWDQFH 89YLV RI b 3G3 b 2'3$ RQ D ZDWHU VXESKDVH 0HDQ PROHFXODU DUHD YV UDWLR RI 2'3$3RUSK\ULQ $f 3G3 %f 3G3O 7UDQVPLVVLRQ 89YLV RI 3G3 ILOPV WUDQVIHUUHG DW KLJK DQG ORZ 00$ $EVRUEDQFH VFDOH FRUUHVRQGV WR WKH ILOP WUDQVIHUUHG DW ƒ PROHFXOHn 89YLV RI 6$ 3G3 ILOPV ULQVHG LQ KRW &+&, 7UDQVPLVVLRQ 89YLV RI ILOPV RI 3G3O WUDQVIHUUHG DW KLJK DQG ORZ 00$ $EVRUEDQFH RI 6RUHW YV WLPH ULQVHG LQ KRW &+&, $f 3G3 %f 3G3O ,OOXVWUDWLRQ RI RULHQWDWLRQ DQG SDFNLQJ RI 3G3 ILOPV WUDQVIHUUHG DW KLJK DQG ORZ 00$ ,;

PAGE 10

,OOXVWUDWLRQ RI RULHQWDWLRQ DQG SDFNLQJ RI 3G3 ILOPV WUDQVIHUUHG DW KLJK DQG ORZ 00$ 6WUXFWXUHV RI $f 0Q3 DQG %f 0Q32 89YLV RI 0Q32 LQ &+& 6ROYHQW EHKDYLRU RI 0Q3 LQ ZDWHU (W2+ DQG &+&, 89YLV FRQFHQWUDWLRQ VWXG\ RI 0Q3 LQ &+&, Df n 0 Ef n 0 0Q32 LQ &+&, [ n 0f ZLWK HWK\OSKRVSKRQLF DFLG Df SXUH 0Q32 Ef[ 0 HWK\OSKRVSKRQLF DFLG Ff [ 0 HWK\OSKRVSKRQLF DFLG Gf [ 0 HWK\OSKRVSKRQLF DFLG Hf SXUH 0Q3 6ROXWLRQ 89YLV LQYHVWLJDWLRQ RI 0Q3fV VHQVLWLYLW\ WR GLVSODFHPHQW RI 5322+f E\ FKORULGH DW [ n 0 7KH DUURZV LQGLFDWH WKH FKDQJHV LQ WKH LQWHQVLW\ RI WKH SHDNV DV WKH FKORULGH FRQFHQWUDWLRQ FKDQJHV IURP 0 WR 0 ZKLOH WKH FRQFHQWUDWLRQ RI 0Q3 VWD\ FRQVWDQW LQ &+&, ,VRWKHUP RI 0Q3 RQ ZDWHU VXESKDVH 5HIOHFWDQFH 89YLV RI 0Q3 RQ ZDWHU VXESKDVH 89YLV RI 0Q3 FDSSLQJ OD\HUV WUDQVIHUUHG RQWR 2'3$=U DW GLIIHUHQW VXUIDFH SUHVVXUHV LQGLFDWHG E\ WKH DUURZVf /% ILOPV RI 0Q3 WUDQVIHUUHG DW $f P1P DQG %f P1P ULQVHG LQ &+&, 0Q3 WUDQVIHUUHG E\ /% DW P1 Pn DQG ULQVHG LQ &+&1 $f WUDQVIHUUHG IURP D PJ P/n VROXWLRQ 0Q3 WUDQVIHUUHG IURP 0 >&I@ DTXHRXV VXESKDVH DW P1 Pn 0Q3 VHOIDVVHPEOHG IURP (W2+3/2 DQG ULQVHG LQ &+&, 7KH OHJHQG LQGLFDWHV WKH VSHFWUD DIWHU ULQVLQJ DIWHU EHLQJ OHIW RYHUQLJKW DQG WKH ULQVHG DJDLQ RYHU D WKUHH GD\ SHULRG 6$ 0Q3 ILOPV ZLWK ULQVLQJ LQ KRW &+&1 89YLV UHVSRQVH RI D 6$ 0Q3 ILOP GXULQJ ULQVLQJ ZLWK KRW &+&1 89YLV RI 0Q3 VHOIDVVHPEOHG ILOPV EHIRUH DQG DIWHU ULQVLQJ LQ KRW (W2+ 0Q3 VHOIDVVHPEOHG IURP D 0 FKORULGH VROXWLRQ [

PAGE 11

;36 RI 0Q3 6$ ILOP 7KH LQVHUW LV DQ HQODUJHG YLHZ RI WKH VDPH VSHFWUXP EHWZHHQ DQG H9 6WUXFWXUHV RI $f 0Q3 %f 0Q32 &f ,P2'3$ DQG 'f ,P+ 6LPSOLILHG 6FKHPDWLF RI 0Q3 DQG ,P2'3$ LQFRUSRUDWLRQ LQ ILOPV 6ROYHQW UHVSRQVH RI $f 0Q32 DQG %f 0Q3 WR ,P+ 6ROYHQW UHVSRQVH RI $f 0Q32 DQG %f 0Q3 WR ,P2'3$ /HJHQGV LQGLFDWH WKH PRODU UDWLR RI 0Q3 WR ,P2'3$ 89YLV RI 2'3$=U+'3$ 6$ 0Q3 ILOP ULQVHG LQ KRW &+& 0Q3 VXEVWLWXWHG RQWR ,P2'3$+'3$ /% ILOPV DIWHU &+&, ULQVLQJ 0Q3 VXEVWLWXWHG RQWR D b ,P2'3$+'3$ ILOP ULQVHG LQ URRP WHPSHUDWXUH DQG KRW &+&, 8
PAGE 12

;36 PXOWLSOH[ VFDQ RI 1 V UHJLRQ RI ,P2'3$0Q3 ILOP VHOIDVVHPEOHG RXW RI &+&, VROXWLRQ 7KH GDVKHG OLQHV UHSUHVHQW WKH *DXVVLDQ SHDN ILWV ;36 PXOWLSOH[ VFDQ RI ,P2'3$0Q3 ILOP VHOIDVVHPEOHG IURP D PL[WXUH LQ (W2+)/2 $75,5 RI ,P2'3$ 6$ ILOP ,QFUHDVH LQ DEVRUEDQFH LQWHQVLW\ RI FPn SHDN LQ ,P2'3$ ZLWK 6$ WLPH $75,5 RI DON\O UHJLRQ RI $f 0Q3 VXEVWLWXWHG RQ D b ,P2'3$ EDVH FDSSLQJ OD\HU %f 0Q3 VXEVWLWXWHG RQ D b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

PAGE 13

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f DQG VHOIDVVHPEO\ 6$f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

PAGE 14

LQWHUDFWLRQ LQ WKH ILOPV %HFDXVH FKURPRSKRUH DJJUHJDWLRQ ZDV H[SHFWHG WR LQKLELW FDWDO\VLV ILOP SUHSDUDWLRQ FRQGLWLRQV ZHUH VRXJKW LQ RUGHU WR DYRLG WKLV /% DQG 6$ ILOPV RI SXUH PDQJDQHVH SRUSK\ULQV ZHUH VXFFHVVIXOO\ SUHSDUHG E\ D QXPEHU RI GLIIHUHQW PHWKRGV $JJUHJDWLRQ DSSHDUHG LQVLJQLILFDQW ZKHQ WUDQVIHUUHG DW KLJK PHDQ PROHFXODU DUHDV DQG ZKHQ WKH ILOPV ZHUH VHOIDVVHPEOHG 7KH SXUH PDQJDQHVH SRUSK\ULQ ILOPV ZHUH VXFFHVVIXO DW FDWDO\]LQJ WKH HSR[LGDWLRQ RI F\FORRFWHQH XVLQJ LRGRV\OEHQ]HQH DV WKH R[LGDQW 7R DFWLYDWH WKH SRUSK\ULQ IRU FDWDO\VLV ZLWK SHUR[LGH R[LGDQWV D KHWHURF\FOLF OLJDQG ZDV DOVR LQFRUSRUDWHG LQWR WKH PDQJDQHVH SRUSK\ULQ FRQWDLQLQJ ILOPV 7KH KHWHURF\FOLF OLJDQG XVHG ZDV DQ LPLGD]ROH VXEVWLWXWHG ZLWK DQ RFWDGHF\OSKRVSKRQLF DFLG FKDLQ %RWK WKH PDQJDQHVH SRUSK\ULQ DQG WKH LPLGD]ROH DPSKLSKLOH ZHUH WHWKHUHG WR D ]LUFRQLXP SKRVSKRQDWH QHWZRUN ILUVW IRU HDVH RI ILOP V\QWKHVLV DQG VHFRQG WR VWDELOL]H WKH ILOP IRU XVH LQ WKH FDWDO\VLV UHDFWLRQV 7KRXJK VLJQLILFDQW FDWDO\VW GHJUDGDWLRQ KDV EHHQ UHSRUWHG LQ KRPRJHQHRXV DQG DOWHUQDWLYH KHWHURJHQHRXV FDWDO\VLV VWXGLHV WKH PDQJDQHVH SRUSK\ULQ DQG LPLGD]ROH FRQWDLQLQJ ]LUFRQLXP SKRVSKRQDWH ILOPV ZHUH JHQHUDOO\ PRUH UHVLVWDQW WR GHJUDGDWLRQ XQGHU FDWDO\VLV FRQGLWLRQV 7KH VWDELOLW\ RI WKH ILOPV WRZDUG HSR[LGDWLRQ FRQGLWLRQV KDV OHG WR HDVLO\ UHF\FODEOH FDWDO\VWV [LY

PAGE 15

&+$37(5 ,1752'8&7,21 8OWUDWKLQ )LOPV 7KH VWXG\ RI XOWUDWKLQ ILOPV HVSHFLDOO\ PRQRPROHFXODU WKLFN ILOPV HQDEOHV WKH VWXG\ RI WZRGLPHQVLRQDO V\VWHPV DQG DOORZV WKH VLPSOLILFDWLRQ RI FRPSOLFDWHG WKHUPRG\QDPLF EHKDYLRUV 5HFHQW LQWHUHVW LQ PRQROD\HUV DQG PXOWLOD\HUV IRFXVHV RQ WKH PDQ\ SRWHQWLDO DSSOLFDWLRQV RI RUJDQL]HG DQG IXQFWLRQDO WKLQ ILOPV ZKLFK LQFOXGH RSWRHOHFWURQLFV FRDWLQJVn FKHPLFDO VHQVRUV If DQG KHWHURJHQHRXV FDWDO\VWVn ,Q RUGHU WR SUHSDUH WKHVH RUJDQL]HG DQG HVVHQWLDOO\ WZRGLPHQVLRQDO VWUXFWXUHV WKH /DQJPXLU%ORGJHWW /%f DQG VHOIDVVHPEO\ 6$f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nV VWXGLHV DW *( /DERUDWRULHV DQG KHQFH KLV QDPH LV DVVRFLDWHG ZLWK D IXQGDPHQWDO PHWKRG RI SUHSDULQJ RUJDQL]HG PRQRPROHFXODU WKLFN

PAGE 16

ILOPV +LV DVVRFLDWH .DWKHULQH %ORGJHWW ILUVW WUDQVIHUUHG WKHVH ILOPV IURP WKH ZDWHU VXUIDFH RQWR VROLG VXSSRUWV 7KH 6$ WHFKQLTXH ZDV ILUVW GHVFULEHG LQ VFLHQWLILF UHSRUWV LQ WKH ODWH fV DQG PLG nVf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f LV GLFWDWHG VROHO\ E\ WKH JHRPHWU\ RI WKH DFWLYH VLWHV RQ WKH VXUIDFH +RZHYHU LQ /% ILOPV WKH SUHVVXUH DQG DUHD RI GHSRVLWLRQ FDQ EH VHOHFWHG WR GHSRVLW D SDUWLFXODU SKDVH RI WKH PRQROD\HU DQG WR LQIOXHQFH WKH WUDQVIHUUHG ILOP RUJDQL]DWLRQ $Q XQGHUVWDQGLQJ

PAGE 17

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n
PAGE 18

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f )LJXUH f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f )LJXUH f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

PAGE 19

00$ $ PROHFXOHnf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

PAGE 20

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

PAGE 21

D PLUURU RQ WKH EDVH RI WKH WURXJK DQG UHIOHFWLQJ D EHDP WKURXJK WKH PRQROD\HU RQWR WKLV PLUURU DQG EDFN LQWR D GHWHFWRU 7KHVH VWXGLHV FDQ KHOS GHWHUPLQH WKH RQVHW RI DJJUHJDWLRQ LQ ILOPV ZLWK VXFK D WHQGHQF\ /O /DQJPXLU%ORGJHWW ILOP IRUPDWLRQ /% ILOPV DUH IRUPHG E\ YHUWLFDOO\ WUDQVIHUULQJ /DQJPXLU PRQROD\HUV IURP WKH ZDWHU VXUIDFH RQWR D VROLG VXSSRUW 7KHUH DUH WKUHH FRPPRQ YHUWLFDO GLSSLQJ WHFKQLTXHV ZKLFK IRUP ; < DQG =W\SH ILOPV )LJXUH f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
PAGE 22

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fV ODZ (TXDWLRQ f QO FVLQ" f ZKHUH Q LV DQ LQWHJHU $ LV WKH ZDYHOHQJWK RI WKH UDGLDWLRQ G LV WKH LQWHUOD\HU VSDFLQJ DQG LV WKH DQJOH RI LQFLGHQFH DQG UHIOHFWLRQ RI WKH EHDP ,GHDOO\ WKHUH VKRXOG EH D VLJQLILFDQW GLIIHUHQFH EHWZHHQ WKH HOHFWURQ GHQVLW\ RI WKH KHDG JURXS DQG WKDW RI WKH K\GURSKRELF UHJLRQ DOORZLQJ ;UD\ GLIIUDFWLRQ SHDNV WR

PAGE 23

EH REVHUYHG LQ /% ILOPV 7KH GVSDFLQJ ZKLFK TXDQWLILHV WKH SHULRGLFLW\ EHWZHHQ SODQHV RI KLJK HOHFWURQ GHQVLW\ WKHUHIRUH LV WKH PHDVXUH RI WKH GLVWDQFH EHWZHHQ KHDG JURXSV 7KLV WHFKQLTXH LV YHU\ VHQVLWLYH WR ORQJUDQJH SHULRGLFLW\ DQG PDQ\ QDUURZ SHDNV DUH W\SLFDOO\ LQGLFDWLYH RI D ZHOOGHILQHG OD\HUHG DUFKLWHFWXUH )LJXUH f )LJXUH ;UD\ GLIIUDFWLRQ GLDJUDP 7R VWXG\ WKH FKHPLFDO PDNHXS RI WKH VXUIDFH DWWHQXDWHG WRWDO UHIOHFWDQFH )7,5 $75f DQG ;UD\ SKRWRHOHFWURQ VSHFWURVFRS\ ;36f DUH HPSOR\HG $75 VWXGLHV LQYROYH WUDQVIHUULQJ D ILOP RQWR D FU\VWDO VXFK DV SDUDOOHORJUDPVKDSHG JHUPDQLXP RU VLOLFRQ FU\VWDO ZLWK HQGV FXW DW r DQJOHV 7KLV LV DQ LGHDO PHWKRG IRU UHFRUGLQJ WKH ,5 VSHFWUD RI ILOPV EHFDXVH LW DOORZV WKH ILOP WR EH VDPSOHG PDQ\ WLPHV GXH WR WKH LQWHUQDO UHIOHFWLRQ RI WKH ,5 EHDP WKURXJK WKH FU\VWDO $75 DOVR SURYLGHV LQIRUPDWLRQ DERXW WKH VXUIDFH FRYHUDJH DQG SDFNLQJ PRGHV )XUWKHU SRODUL]HG VWXGLHV XVLQJ WKLV WHFKQLTXH FDQ JLYH LQIRUPDWLRQ DERXW WKH ILOP RUJDQL]DWLRQ DQG RULHQWDWLRQ )LJXUH f %DFNJURXQG LQIRUPDWLRQ SHUWDLQLQJ WR ILOPV VWXGLHG E\ $75,5 DOORZV

PAGE 24

HOXFLGDWLRQ RI LQIRUPDWLRQ DERXW ILOPV FRQWDLQLQJ QHZ DPSKLSKLOHV )RU H[DPSOH E\ FRPSDULQJ WKH DUHDV RI WKH DON\O VWUHWFKHV RI D QHZ DPSKLSKLOH WR WKDW RI ZHOO XQGHUVWRRG IDWW\DFLG ILOPV DQ LGHD RI WKH WUDQVIHU TXDOLW\ FDQ EH REWDLQHG 7KLV WRRO LV SDUWLFXODUO\ KHOSIXO LQ VWXG\LQJ PRQROD\HUV ZLWK WUDQVIHU UDWLRV YDU\LQJ IURP XQLW\ $75)7,5 FDQ DOVR LQGLFDWH WKH SDFNLQJ QDWXUH RI WKH DON\O FKDLQV ,I WKH FKDLQV DUH LQ D PRVWO\ WUDP FRQILJXUDWLRQ DQG FORVHSDFNHG WKH DV\PPHWULF &+ VWUHWFK YD&+f ZLOO RFFXU DW FPn DQG KDYH D IXOO ZLGWK DW LWV KDOI PD[LPXP ):+0f RI FD FPn 7KH V\PPHWULF &+ VWUHWFK YV&+f ZLOO RFFXU DW FD FPn ,I WKHUH DUH D VLJQLILFDQW QXPEHU RI JDXFKH LQWHUDFWLRQV LQ WKH FKDLQV WKH YD&+ DQG YV&+ VWUHWFKHV ZLOO VKLIW WR KLJKHU HQHUJLHV FD FPn IRU WKH YD&+ DQG FD FPr IRU WKH YD&+ VWUHWFKHVff ;2•••• )LJXUH 6FKHPDWLF RI WKH $75,5 ([SHULPHQW ;36 LV D PHWKRG XVHG WR GHWHUPLQH WKH HOHPHQWDO PDNHXS DQG SRVVLEO\ DWRPLF SURSRUWLRQV ZLWKLQ D ILOP EDVHG RQ WKH SKRWRHOHFWURQ HIIHFW ;36 PHDVXUHV WKH HQHUJ\ RI DQ H[SHOOHG HOHFWURQ DV WKH VXUIDFH LV ERPEDUGHG ZLWK D PRQRFKURPDWLF ; UDGLDWLRQ VRXUFH )LJXUH f :KHQ D KLJKHQHUJ\ VRXUFH LV DSSOLHG WKH NLQHWLF HQHUJ\

PAGE 25

RI WKH HPLWWHG HOHFWURQV FDQ EH UHODWHG WR WKH H[FHVV HQHUJ\ DQG WR WKH VWUHQJWK RI WKH HOHFWURQfV ELQGLQJ E\ (TXDWLRQ ZKLFK LV WKH (LQVWHLQ SKRWRHOHFWULF ODZ (NLf KYHAf(E f ZKHUH (E LV WKH ELQGLQJ HQHUJ\ H LV WKH FKDUJH RI WKH HOHFWURQ K LV 3ODQFNfV FRQVWDQW Y LV WKH IUHTXHQF\ RI WKH UDGLDWLRQ DQG LV WKH ZRUN IXQFWLRQ FRUUHVSRQGLQJ WR WKH PLQLPXP HQHUJ\ UHTXLUHG IRU HMHFWLRQ RI DQ HOHFWURQ 'HWHFWRU (NLQ r KY 0RQRFKURPDWLF ;UD\ 5HDP )LJXUH 6FKHPDWLF RI ;36 H[SHULPHQW 7KH ;36 VSHFWUXP SORWV HOHFWURQ FRXQWV YHUVXV ELQGLQJ HQHUJ\ %LQGLQJ HQHUJLHV DUH XQLTXH WR HDFK HOHPHQW SUHVHQW LQ WKH ILOP DV ZHOO DV WR WKDW HOHPHQWf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

PAGE 26

VSHFWUXP 7KHVH WZR SHDNV ZHUH DVVRFLDWHG ZLWK WKH GLIIHUHQW QLWURJHQ HQYLURQPHQWV LQ WKH LPLGD]ROH DQG SRUSK\ULQ FOHDUO\ LQGLFDWLQJ WKDW ERWK VSHFLHV ZHUH SUHVHQW LQ WKH PL[HG ILOP 7KH LQWHQVLWLHV RI WKH ;36 SHDNV FDQ EH XVHG WR GHWHUPLQH WKH UHODWLYH UDWLRV RI WKH HOHPHQWV SUHVHQW DQG FDQ LQGLFDWH WKH W\SH RI FU\VWDOOLQH ODWWLFH IRUPHG +RZHYHU WKH LQWHQVLWLHV RI WKH ;36 SHDNV DUH VHQVLWLYH WR PDQ\ SDUDPHWHUV VXFK DV WKH HOHPHQWfV HOHFWURQ HVFDSH GHSWK ZKLFK FDQ FRPSOLFDWH WKH GHWHUPLQDWLRQ RI WKH HOHPHQWDO UDWLRV ,Q D JLYHQ VDPSOH WKH REVHUYHG UHODWLYH SHDN LQWHQVLWLHV DUH FRPSDUHG WR D FDOFXODWHG YDOXH EDVHG RQ (TXDWLRQ / =H[S GfL ƒH$^VPf L=H[S aGP OH[3 f§ G P ƒH$^VLQGf ILVLQf f ZKHUH ,$ LV WKH UHODWLYH LQWHQVLW\ RI HOHPHQW $ ,$rr LV WKH DWRPLF VHQVLWLYLW\ IDFWRU GP LV WKH RYHUOD\HU WKLFNQHVV LV WKH LQFLGHQW DQJOH RI WKH ;UD\ EHDP DQG $H LV WKH LQHODVWLF PHDQ IUHH SDWK 7KH LQHODVWLF PHDQ IUHH SDWK UHSUHVHQWV WKH GLVWDQFH RYHU ZKLFK b RI WKH HOHFWURQV FDQ WUDYHO EHIRUH LQWHUHOHFWURQ FROOLVLRQV OHDG WR D ORVV RI HQHUJ\ DQG LV GHILQHG E\ >AQ f e:Qf@ ƒf f 89YLV VSHFWURVFRS\ UHYHDOV D ILOPfV RSWLFDO EHKDYLRU 7\SLFDOO\ ILOPV DUH WUDQVIHUUHG RQWR JODVV RU TXDUW] VXEVWUDWHV DQG WUDQVPLWWDQFH VWXGLHV DUH SHUIRUPHG

PAGE 27

8VLQJ SRODUL]HUV DQG VWDJHV WKDW DOORZ FDUHIXO SODFHPHQW RI WKH VXEVWUDWHV DW GLIIHUHQW DQJOHV RI LQFLGHQFH WR WKH EHDP WKH RULHQWDWLRQ RI WKH FKURPRSKRUHV ZLWKLQ WKH ILOPV FDQ EH GHWHUPLQHG %\ FRPSDULQJ WKH DEVRUEDQFH LQWHQVLW\ LQ WKH V DQG S SRODUL]DWLRQ D GLFKURLF UDWLR FDQ EH FDOFXODWHG XVLQJ (TXDWLRQ M f 3 2ULHQWDWLRQDO RUGHU ZLWKLQ WKH SODQH RI WKH ILOP DQG VXEVWUDWH LV REWDLQHG E\ ORRNLQJ DW UHVXOWV IURP r DQG V DQG Sf SRODUL]DWLRQ DV WKH EHDP LV QRUPDO WR WKH VXUIDFH r DQJOH RI LQFLGHQFHf 6WXG\LQJ WKH SRODUL]DWLRQ DW KLJKHU DQJOHV RI LQFLGHQFH W\SLFDOO\ rf HQDEOHV WKH GHWHUPLQDWLRQ RI WKH RULHQWDWLRQ RXW RI WKH SODQH )LJXUH f r SRODUL]DWLRQ )LJXUH 6FKHPDWLF RI SRODUL]HG 89YLV H[SHULPHQWDO EHDP GLUHFWLRQV

PAGE 28

7KH GLFKURLF UDWLR FDQ EH XVHG WR GHWHUPLQH WKH FKURPRSKRUH RULHQWDWLRQ LQ D ILOP ,Q WKH FDVH RI ILOPV FRQWDLQLQJ SRUSK\ULQ FKURPRSKRUHV 2UULW HW DO GHWHUPLQHG WKDW WKH GLFKURLF UDWLR FDQ EH WUDQVODWHG LQWR DQ RULHQWDWLRQ SDUDPHWHU 3f XVLQJ WKH JUDSK VKRZQ LQ )LJXUH DQG KHQFH DQ RULHQWDWLRQ DQJOH f FDQ EH HVWDEOLVKHG XVLQJ (TXDWLRQ 3 FRV Gf f UHSUHVHQWV WKH DQJHO EHWZHHQ WKH VXUIDFH QRUPDO DQG WKH FKURPRSKRUHfV PROHFXODU SODQH $V LV RIWHQ REVHUYHG ZLWKLQ WKH SODQH RI D ILOP FRQWDLQLQJ SRUSK\ULQV LI LV XQLW\ WKHUH LV QR SUHIHUUHG RULHQWDWLRQ ,I 3 DQG WKHUHIRUH DV PHDVXUHG IURP WKH VXUIDFH QRUPDO 4 2ULHQWDWLRQ 3DUDPHWHU 3f )LJXUH %HKDYLRU RI WKH REOLTXH GLFKURLF UDWLR YHUVXV DQ RULHQWDWLRQ SDUDPHWHU 3f

PAGE 29

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f RQ K\GUR[\ODWHG VXUIDFHV VXFK DV JODVV WR IRUP D VLOR[DQH SRO\PHU 0XOWLOD\HUV ZHUH SURGXFHG LI WKH DPSKLSKLOH ZDV WHUPLQDWHG DW ERWK D DQG FR SRVLWLRQV E\ VXUIDFHDFWLYH JURXSV :KHQ D DQG WR SRVLWLRQV ZHUH WZR GLIIHUHQW IXQFWLRQDOLWLHV VXEVHTXHQW GLSSLQJ LQ VHOI DVVHPEO\ VROXWLRQV SURGXFHG QRQFHQWURV\PPHWULF ILOPV 8QIRUWXQDWHO\ VWXGLHV KDYH VKRZQ WKDW VPDOO GHIHFWV LQ WKH HDUO\ OD\HUV FDQ PDJQLI\ XSRQ PXOWLOD\HU IRUPDWLRQ VXFK WKDW QHDUO\ DOO RUGHU EUHDNV GRZQ E\ WKH WHQWK OD\HU 7KH 6$ RI 276 LV QRZ FRPPRQO\ XVHG IRU K\GURSKRELVL]LQJ JODVV VOLGHV IRU /% VXEVWUDWHV 7KH FKHPLVRUSWLRQ RI WKLROV RQ JROG ZDV LQLWLDWHG E\ 1X]]R DQG $OLDUD DQG FRQWLQXHG E\ 3RUWHU :KLWHVLGHV DQG RWKHUV $ON\O WKLROV LQ ZKLFK WKH FKDLQ OHQJWKV UDQJH IURP RQH FDUERQ WR RYHU WZHQW\ KDYH EHHQ VWXGLHG &ORVHO\ SDFNHG OD\HUV ZHUH REVHUYHG ZKHQ WKH FKDLQ OHQJWK H[FHHGHG HOHYHQ FDUERQV 7KH JROG VXUIDFH XVHG LQ WKHVH VWXGLHV ZDV IRUPHG E\ YDFXXP HYDSRUDWLRQ RQWR FOHDYHG DONDOL

PAGE 30

PHWDO KDOLGH VXUIDFHV 0DQ\ RI WKH VXUIDFWDQWV VWXGLHG E\ VHOIDVVHPEO\ GLG QRW IRUP VWDEOH PRQROD\HUV RQ DTXHRXV VXESKDVHV DQG WKHUHIRUH FRXOG QRW EH VWXGLHG E\ WKH /% PHWKRG +RZHYHU WKHVH VXUIDFWDQWV ZHUH HDVLO\ VWXGLHG E\ WKH 6$ PHWKRG +\EULG 2UJDQLF,QRUJDQLF 8OWUDWKLQ )LOPV %DVHG RQ /D\HUHG 6ROLGV %DFNJURXQG $ QHZ FODVV RI /% ILOPV KDV EHHQ GHYHORSHG ZKLFK LQFRUSRUDWH DQ LQRUJDQLF PHWDO SKRVSKRQDWH QHWZRUN LQWR WKH SRODU UHJLRQfr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r 7KH LQWHUHVW LQ WKH PHWDO SKRVSKRQDWHV ZDV VSDUNHG E\ WKHLU SRWHQWLDO DV LQRUJDQLF LRQ H[FKDQJH PDWHULDOVr KRZHYHU WKH RUJDQLF UHJLRQ FDQ DOVR EH PRGLILHG DQG IXQFWLRQDOL]HG SURYLGLQJ D VWUDLJKWIRUZDUG PHWKRG IRU SUHSDULQJ D ZLGH YDULHW\ RI PDWHULDOV

PAGE 31

=LUFRQLXP 3KRVSKRQDWH VROLGV &OHDUILHOG SXEOLVKHG HDUO\ ZRUN RQ PHWDO SKRVSKRQDWHV DQG SKRVSKDWHV LQ WKH fV 7KH IRFXV DW WKLV WLPH ZDV RQ WKH ]LUFRQLXP VROLGV ZKLFK IRUP WZR SUHIHUUHG SKDVHV D DQG \ ZKLFK KDYH WKH FRPSRVLWLRQV =U+3f+ DQG =U3f+3f+ UHVSHFWLYHO\ ,Q WKHVH OD\HUHG PDWHULDOV D WZRGLPHQVLRQDO PHWDO ODWWLFH LV IRUPHG DQG VHSDUDWHG IURP DQ DGMDFHQW PHWDO ODWWLFH E\ WKH RUJDQLF OD\HU LQ WKH SKRVSKRQDWHV RU E\ WKH K\GURJHQ ERQGV IURP WKH IRXUWK K\GUR[\ VLWH LQ WKH SKRVSKDWHV 7KH LQWHUOD\HU DUHD LQ WKHVH VROLGV IRUPV D SRVVLEOH GRPDLQ IRU LQWHUFDODWLRQ RI LQRUJDQLF PDWHULDOV VXFK DV DPLQHV f Lr 2 R )LJXUH &U\VWDO VWUXFWXUH RI ]LUFRQLXP SKRVSKDWH 7KH FU\VWDO VWUXFWXUH RI WKH =USKHQ\OSKRVSKRQDWH VROLG ZDV GHWHUPLQHG LQ WKH nV DQG IRXQG WR IRUP D VWUXFWXUH VLPLODU WR WKH DSKDVH 6XEVHTXHQW VWXGLHV UHYHDOHG WKDW DQ\ DON\O RU DU\O JURXS ZKRVH DUHD ZDV XQGHU ƒ ZRXOG IRUP DQ LGHQWLFDO PHWDO ODWWLFH VWUXFWXUH ZKLOH RQO\ WKH LQWHUOD\HU GLVWDQFH FKDQJHG ,Q WKH Q

PAGE 32

DON\O SKRVSKRQDWHV LW ZDV IRXQG WKDW WKHUH LV D WLOW DQJOH LQ WKH FKDLQV RI EHWZHHQ r DQG r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f+ IRU 0J 0Q =Q &D DQG &G ,Q WKHVH PDWHULDOV OD\HUV RI WKH PHWDO DWRPV DUH RFWDKHGUDOO\ FRRUGLQDWHG E\ ILYH SKRVSKRQDWH R[\JHQV DQG RQH ZDWHU PROHFXOH ZLWK HDFK SKRVSKRQDWH JURXS FRRUGLQDWLQJ IRXU PHWDO DWRPV PDNLQJ D FURVVOLQNHG 0 QHWZRUN $ VHFRQG VWUXFWXUH WKH RUWKRUKRPELF 0Q+35f ZDV REVHUYHG IRU WKH &D SKRVSKRQDWHV $ VWUXFWXUDO H[FHSWLRQ WR WKH

PAGE 33

DERYH GLYDOHQW VHULHV LV &X,,f! 7KH &X DWRPV LQ WKHVH SKRVSKRQDWH PDWHULDOV DUH ILYH FRRUGLQDWH DQG IRUP D GLVWRUWHG WHWUDJRQDO S\UDPLGDO JHRPHWU\ 0DOORXN KDV SUHSDUHG D VHULHV RI ODQWKDQLGH SKRVSKRQDWHV 7KH VWUXFWXUH RI WKHVH PDWHULDOV LV JLYHQ DV /Q,,,f+35f ZKHUH /Q UHSUHVHQWV /D 6P RU &H 7KH ODQWKDQLGHVHULHV SKRVSKRQDWHV DUH PRUH VROXEOH WKDQ WKH ]LUFRQLXP VROLGV EXW OHVV VROXEOH WKDQ WKH GLYDOHQW PDWHULDOV 7KHUHIRUH VLQJOH FU\VWDO GDWD ZDV QRW HDVLO\ REWDLQHGf $75,5 SURYLGHV D IDFLOH PHWKRG IRU FKDUDFWHUL]DWLRQ RI WKH PHWDO SKRVSKRQDWH ODWWLFH IRUPDWLRQ 9LEUDWLRQDO PRGHV DVVLJQHG WR WKH SKRVSKRQDWH DUH H[WUHPHO\ VHQVLWLYH WR WKH PRGH RI PHWDO ELQGLQJ 7KRPDV HW DO KDYH DVVLJQHG WKH YD&+f YLEUDWLRQDO IUHTXHQFLHV IRU WKH GLYDOHQW PHWDOSKRVSKRQDWHV WR EH LQ WKH UDQJH RI FD FP ZKHUH WKH YV&+f VWUHWFKHV RFFXU FD FPn (DFK PHWDO SKRVSKRQDWH PDWHULDO KDV FKDUDFWHULVWLF VWUHWFKHV LQ WKHVH UHJLRQV 6HOI$VVHPEOHG )LOPV ,QFRUSRUDWLQJ 0HWDO 3KRVSKRQDWH %LQGLQJ $IWHU 6DJLYnV ZRUN ZLWK VHOIDVVHPEOLQJ ILOPV RI RFWDGHF\OWULFKORURVLODQH 276f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

PAGE 34

VXEVHTXHQWO\ PHWDOODWHG DQG WKH F\FOH FRQWLQXHG XQWLO PXOWLOD\HUHG ILOPV ZHUH IDEULFDWHG 7KH VHOIDVVHPEO\ RI PHWDO SKRVSKRQDWH ILOPV LV PDGH SRVVLEOH E\ D YHU\ VWURQJ DWWUDFWLRQ EHWZHHQ FHUWDLQ PHWDO LRQV SDUWLFXODUO\ WKH WHWUDYDOHQW PHWDOV VXFK DV =U IRU WKH SKRVSKRQDWH JURXSV RI DON\O SKRVSKRQLF DFLGVf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r 0HWDO SKRVSKRQDWH UHJLRQ )LJXUH &RPSDULVRQ EHWZHHQ $f WUDGLWLRQDO /% ILOPV DQG %f PHWDOSKRVSKRQDWH /% ILOPV

PAGE 35

7KH ]LUFRQLXP PHWDOV KDYH VXFK D KLJK R[RSKLOLFLW\ IRU WKH SKRVSKRQDWH R[\JHQV WKDW ZKHQ D SKRVSKRQLF DFLG DPSKLSKLOH LV VSUHDG RQ WKH VXUIDFH RI D ]LUFRQLXP FDWLRQ FRQWDLQLQJ DTXHRXV VXESKDVH WKH PRQROD\HU FU\VWDOOL]HV EHIRUH LW FDQ EH WUDQVIHUUHG 7KHUHIRUH D WKUHHVWHS GHSRVLWLRQ SURFHGXUH KDV EHHQ GHYHORSHG $ SKRVSKRQLF DFLG FRQWDLQLQJ PRQROD\HU LV IRUPHG RQ WKH VXUIDFH RI D SXUH ZDWHU VXESKDVH DQG WUDQVIHUUHG RQWR D K\GURSKRELF VXEVWUDWH 2QWR WKLV SKRVSKRQLF DFLG VXUIDFH D OD\HU RI ]LUFRQLXP LV DVVHPEOHG IROORZHG E\ WKH WUDQVIHU RI D VHFRQG /% PRQROD\HU FRQWDLQLQJ D SKRVSKRQLF DFLG 7KLV WKUHHVWHS GHSRVLWLRQ WHFKQLTXH ZLOO EH GHVFULEHG LQ GHWDLO LQ &KDSWHU $GYDQWDJHV RI WKLV WKUHHVWHS WHFKQLTXH LQFOXGH WKH IDFW WKDW DW WKH K\GURSKLOLF VWDJH WKH PRQROD\HU LV VWDEOH DQG FDQ EH LQGHSHQGHQWO\ FKDUDFWHUL]HG E\ $75)7,5 RU ;36 HWF 6HFRQG WKLV PHWKRG DOORZV WKH IRUPDWLRQ RI DOWHUQDWLQJ ILOPV LQ ZKLFK WKH WHPSODWH DQG FDSSLQJ OD\HUV GR QRW KDYH WR EH IRUPHG RI WKH VDPH DPSKLSKLOH 7KH RSWLRQ RI IRUPLQJ DOWHUQDWLQJ ILOPV LV LPSRUWDQW EHFDXVH VRPH DPSKLSKLOHV GR QRW WUDQVIHU RQ WKH GRZQ VWURNH EXW ZLOO WUDQVIHU RQWR DQ 2'3$ WHPSODWH OD\HU $ GLVDGYDQWDJH RI WKH WKUHHVWHS GHSRVLWLRQ RI WKH SKRVSKRQDWH ILOPV RFFXUV DW WKH VHOI DVVHPEO\ RI WKH ]LUFRQLXP ODWWLFH 7KH VHOIDVVHPEO\ RI WKH ]LUFRQLXP RQWR WKH 2'3$ WHPSODWH FDXVHV WKH PHWDO SKRVSKRQDWH ODWWLFH WR EH DPRUSKRXV ZKHUHDV LQ D RQHVWHS GHSRVLWLRQ WKH PHWDO ODWWLFH LV FU\VWDOOLQH $Q DOWHUQDWLYH WHFKQLTXH RI ILOP IRUPDWLRQ LV HPSOR\HG IRU WKH GLYDOHQW DQG WULYDOHQW PHWDOV ,Q WKHVH FDVHV WKH PHWDO VDOWV DUH GLVVROYHG LQ WKH DTXHRXV VXESKDVH WKH SKRVSKRQLF DFLG PRQROD\HU LV IRUPHG RQ WKH VXUIDFH DQG WKH K\GURSKRELF VXEVWUDWH LV GLSSHG GRZQ DQG WKHQ XS WKURXJK WKH VDPH FRPSUHVVHG PRQROD\HU IRUPLQJ D FRPSOHWH PHWDOSKRVSKRQDWH OD\HU RU DQ /% ELOD\HU 7KH FU\VWDOOL]DWLRQ RI WKH PHWDOSKRVSKRQDWH ODWWLFH RFFXUV RQ WKH VORZ XSVWURNH RI WKH ILOP WKURXJK WKH PRQROD\HU )LJXUH f

PAGE 36

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

PAGE 37

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

PAGE 38

%DFNJURXQG RQ 3RUSK\ULQV 2SWLFDO %HKDYLRU RI 3RUSK\ULQV 3RUSK\ULQV DUH D FRPPRQ UHVHDUFK IRFXV LQ SK\VLFV FKHPLVWU\ DQG ELRORJ\ 3K\VLFDO DQG FKHPLFDO LQWHUHVW LQ SRUSK\ULQV VWHPV IRU H[DPSOH IURP WKHLU KLJKO\ FRQMXJDWHG VWUXFWXUH WKDW DOORZV IDFLOH HOHFWURQWUDQVIHU DQG IURP WKHLU FKHPLFDO DFWLYLW\ DW DQ H[SRVHG PHWDO WKDW PD\ EH DFWLYH WRZDUG FDWDO\VLV RU FKHPLFDO VHQVLQJ If %LRORJLVWV DQG ELRFKHPLVWV DUH LQWHUHVWHG LQ WKH FRPPRQ ELRORJLFDO EXLOGLQJ EORFNV WKDW DUH EDVHG RQ WKH SRUSK\ULQ VWUXFWXUH 7KH FRUH VWUXFWXUH RI WKH SRUSK\ULQ LV WKH FRPSOHWHO\ VDWXUDWHG SRUSKLQH PDFURF\FOH )LJXUH f 8SRQ UHGXFLQJ WKLV PDFURF\FOH WR WKH XQVDWXUDWHG IRUP WKH SRUSK\ULQ FKURPRSKRUH LV DFKLHYHG %\ K\GURO\]LQJ RQH RI WKH S\UUROH XQLWV WKH FKORULQ FRPSRXQG LV SUHSDUHG $QRWKHU LPSRUWDQW VWUXFWXUH EDVHG RQ WKH SRUSKLQH FRUH LV WKH SKWKDORF\DQLQH RU WKH WHWUDD]DWHWUDEHQ]SRUSK\ULQ (DFK RI WKHVH VWUXFWXUHV LQFOXGHV HLWKHU WZR SURWRQV DV LQ WKH IUHH EDVH SRUSK\ULQ RU D FRRUGLQDWHG PHWDO ZLWKLQ WKH FHQWHU RI WKH SRUSK\ULQ FDOOHG WKH PHWDOORSRUSK\ULQ ([DPSOHV RI ELRORJLFDOO\ DFWLYH SRUSK\ULQV LQFOXGH FKORURSK\OO ZKLFK LV D PDQJDQHVHFRRUGLQDWHG FKORULQ PROHFXOH DQG KHPH ZKLFK LV DQ LURQVXEVWLWXWHG SRUSK\ULQ

PAGE 39

)LJXUH 6WUXFWXUHV RI SRUSK\ULQW\SH PROHFXOHV $f SRUSKLQH %f IUHH EDVH SRUSK\ULQ DQG &f SWKDORF\DQLQH 3RUSK\ULQV KDYH FKDUDFWHULVWLF DQG VWURQJ RSWLFDO WUDQVLWLRQV E\ ZKLFK WKH\ FDQ EH LGHQWLILHG 7KH EDQGV RIWHQ REVHUYHG LQ YLVLEOH VSHFWUD RI SRUSK\ULQV LQFOXGH WKH % RU 6RUHW %DQG DQG 4 %DQGV DV VHHQ LQ )LJXUH IRU D SDOODGLXP WHWUDSKHQ\OSRUSK\ULQ 3G733f 7KH 6RUHW %DQG LV DVVRFLDWHG ZLWK WKH DOORZHG bQr WUDQVLWLRQ DQG LV W\SLFDOO\ VHHQ EHWZHHQ DQG QP )LJXUH 89YLV VSHFWUXP RI D PHWDOORSRUSK\ULQ 3G733f

PAGE 40

7KH 4%DQGV DUH REVHUYHG EHWZHHQ DQG QP 7KH ORZHU HQHUJ\ 4 %DQG 4Df LV DVVRFLDWHG ZLWK WKH HOHFWURQLF RULJLQ 4f RI WKH ORZHU HQHUJ\ VLQJOHW H[FLWHG VWDWH 7KH KLJKHU HQHUJ\ 4%DQG 4Sf KDV D FRQWULEXWLRQ IURP D YLEUDWLRQ PRGH DQG LV GHQRWHG 4f %RWK 4f DQG 4f DUH TXDVLDOORZHG WUDQVLWLRQV ZLWK UHODWLYHO\ ORZ DEVRUEDQFH LQWHQWLVWLHV 7KH 4%DQGV DUH KLJKO\ VHQVLWLYH WR WKH V\PPHWU\ RI WKH PROHFXOH ,Q SRUSK\ULQV RI 'K V\PPHWU\ VXFK DV PHWDOORSRUSK\ULQV RU WKH GLDFLGLF RU GLEDVLF IRUPV RI WKH SRUSK\ULQ WZR 4 %DQGV DUH REVHUYHG DV SLFWXUHG LQ )LJXUH 7KH IUHHEDVH SRUSK\ULQ LV RI 'K V\PPHWU\ DQG WKH GHJHQHUDF\ RI WKH 4%DQGV LV GLVUXSWHG VSOLWWLQJ WKH 4%DQGV LQWR IRXU SHDNV 7KH DERYH GHVFULEHG WUDQVLWLRQV DUH GXH WR WKH SRUSK\ULQ AHOHFWURQV DQG DUH QQr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f $QRWKHU SRSXODU WKHRU\ LV *RXWHUPDQnV IRXURUELWDO

PAGE 41

PRGHO )LJXUH f ZKLFK FRPELQHV WKH +FNHO02 WKHRU\ ZLWK WKH IUHHHOHFWURQ PRGHO ,Q WKLV PRGHO *RXWHUPDQ GHVFULEHV IRXU RUELWDOV WZR /802V FHJf DQG F HJf HDFK ZLWK ILYH QRGHV ZKLFK DUH GHJHQHUDWH LQ HQHUJ\ DQG WZR +202V EDXf DQG EDOXf HDFK ZLWK IRXU QRGHV ZKLFK DUH QRW GHJHQHUDWH $FFRUGLQJ WR WKH IRXU RUELWDO PRGHO WKH 6RUHW %DQG FRUUHVSRQGV WR WKH WUDQVLWLRQ IURP WKH ORZHU HQHUJ\ DOX RUELWDO WR WKH HJ RUELWDO JLYLQJ D KLJKHU HQHUJ\ WUDQVLWLRQ 7KH 4%DQGV DULVH IURP WKH WUDQVLWLRQ IURP WKH DX RUELWDO ZKLFK LV KLJKHU LQ HQHUJ\ JLYLQJ D ORZHU HQHUJ\ WUDQVLWLRQf )LJXUH *RXWHUPDQfV IRXURUELWDO PRGHO

PAGE 42

+RZHYHU WKHUH DUH DOVR LUUHJXODU SRUSK\ULQV ,UUHJXODU SRUSK\ULQV W\SLFDOO\ PHWDOORSRUSK\ULQV DUH EURNHQ GRZQ LQWR FDWHJRULHV FDOOHG K\SVR DQG K\SHUn SRUSK\ULQV ,Q WKH FDVH RI LUUHJXODU SRUSK\ULQV WKH FHQWUDO PHWDO FRQWDLQV SDUWLDOO\ ILOOHG VKHOOV ZKLFK LQWURGXFH D SRVVLELOLW\ RI PHWDO HOHFWURQV PL[LQJ ZLWK SRUSK\ULQ HOHFWURQV 7KLV PL[LQJ LV FDXVHG E\ WKH SRVVLELOLW\ RI PHWDO WR SRUSK\ULQ EDFNELQGLQJ GXH WR VLPLODU HQHUJLHV RI WKH PHWDOV GRUELWDOV DQG WKH SRUSK\ULQfV WRUELWDOV 7KH FHQWUDO PHWDO LRQ FDQ OHDG WR VLJQLILFDQW FKDQJHV LQ WKH RSWLFDO DQG HPLVVLRQ VSHFWUD 7KH PHWDO DQG LWV R[LGDWLRQ VWDWH GHWHUPLQH ZKLFK FDWHJRU\ WKH SRUSK\ULQnV RSWLFDO EHKDYLRU ZLOO IDOO LQWR $OVR WKH UHOHDVH RI HOHFWURQ GHQVLW\ IURP WKH PHWDO WR WKH SRUSK\ULQ HQDEOHV WKH PHWDO WR VWD\ FRSODQDU ZLWK WKH FKURPRSKRUH DV WKH HIIHFWLYH VL]H RI WKH PHWDO LV UHGXFHG +\SVRSRUSK\ULQV KDYH FHQWUDO PHWDOV RI JURXSV HLJKW WKURXJK HOHYHQ ZLWK FRQILJXUDWLRQV GP ZKHUH P DQG KDYH ILOOHG HJGLf RUELWDOV 7KH LQFOXVLRQ RI WKHVH PHWDO LRQV LV RIWHQ DVVRFLDWHG ZLWK D EDWKRFKURPLF RU EOXH VKLIW UHODWLYH WR WKH FRUUHVSRQGLQJ IUHH EDVH SRUSK\ULQ &RPPRQ K\SVRSRUSK\ULQV LQFOXGH 1L,,f 3G,,f DQG 3W,,fSRUSK\ULQV 7KH 1L,,f SRUSK\ULQV DUH HDVLO\ DIIHFWHG E\ EDVLF D[LDO OLJDQGV ZKHUHDV 3G,,f DQG 3W,,f DUH W\SLFDOO\ IRXU FRRUGLQDWH DQG DSSHDU LQVHQVLWLYH WR WKH SRWHQWLDO OLJDQG HQYLURQPHQW 7KH VHFRQG FODVV RI LUUHJXODU SRUSK\ULQV LV FDOOHG WKH K\SHUSRUSK\ULQV ZKLFK LV IXUWKHU EURNHQ GRZQ LQWR VXEFODVVHV FDOOHG SW\SH GW\SH DQG SVHXGRQRUPDO K\SHUSRUSK\ULQV 0RVW PHWDOORSRUSK\ULQV FODVVLILHG DV K\SHUSRUSK\ULQV KDYH FHQWUDO PHWDOV ZLWK HDVLO\ DFFHVVLEOH ORZHU R[LGDWLRQ VWDWHV 2I WKHVH 0Q,,,f DQG )H,,,f DUH WKH PRVW ZHOO VWXGLHG GXH WR WKHLU ELRORJLFDO LPSOLFDWLRQV 7KH VSHFWUD RI K\SHUSRUSK\ULQV H[KLELW WKH 6RUHW DQG 4%DQGV DV EHIRUH ZLWK VRPH SRVVLEOH VKLIWLQJ $GGLWLRQDO SURPLQHQW DEVRUSWLRQ EDQGV PD\ EH VHHQ W\SLFDOO\ DW KLJKHU HQHUJLHV UHODWLYH WR WKH 6RUHW %DQG 7KH K\SHUSRUSK\ULQ VSHFWUD GHPRQVWUDWH WKH HIIHFWV GXH WR

PAGE 43

PHWDOOLJDQG FKDUJH WUDQVIHU 0/&7f PL[HG ZLWK WKH SRUSK\ULQ KWr WUDQVLWLRQV HYHQ ZLWKLQ WKH 6RUHW %DQG 7KH 0/&7 %DQGV FDQ EH SRUSK\ULQ WR PHWDO PHWDO WR SRUSK\ULQ RU HYHQ D[LDO OLJDQG WR PHWDO 'XH WR WKH VSHFWUDO VHQVLWLYLW\ WR FKURPRSKRUH VXEVWLWXHQWV WR WKH PHWDO LWV R[LGDWLRQ VWDWH DQG WR WKH QDWXUH RI WKH D[LDO OLJDQG DQG WKH DGGLWLRQDO 89YLV %DQGV K\SHUSRUSK\ULQ VSHFWUD DUH PXFK PRUH GLIILFXOW WR DQDO\]H 7KH GW\SH K\SHUSRUSK\ULQV LQFOXGH PHWDOV RI JURXSV VL[ WKURXJK HLJKW 0Q,,,fSRUSK\ULQ IRU H[DPSOH LV G DQG 6 RU KLJKVSLQ DQG LV D FKDUDFWHULVWLF G W\SH SRUSK\ULQ ,Q FKORURIRUP 0Q,,,f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f DXLf WR HJGLf ZKLFK LPSOLHV D QHFHVVLW\ IRU RQH RU PRUH YDFDQFLHV LQ WKH HJGWf RUELWDO RI WKH PHWDO DQG UHGXFWLRQ SRWHQWLDOV ZKLFK DUH QRW WRR QHJDWLYH )LQDOO\ SVHXGRQRUPDO K\SHUSRUSK\ULQV LQFOXGH 92,9f &U,,f 0Q,,f 0R,9f /D DQG $F ZKHUH 6 r 7KHVH PHWDOV VKRZ QRUPDO DEVRUSWLRQ VSHFWUD ZLWK D ZHDN H[WUD DEVRUSWLRQ SRVVLEOH LQ WKH IDUUHG UHJLRQ $OO RI WKHVH PHWDOV KDYH D SDUWLDOO\ ILOOHG RU HPSW\ HJGLf RUELWDO EXW FKDUJHWUDQVIHUV IURP WKH SRUSK\ULQ WR WKH PHWDO DUH WRR KLJK LQ HQHUJ\ WR EH REVHUYHG LQ WKH 89YLV UHJLRQ ,Q DGGLWLRQ IXUWKHU UHGXFWLRQ WDNHV WKHVH PHWDOV WR XQVWDEOH R[LGDWLRQ VWDWHV ZKLFK PDNHV WKLV DQ HYHQ KLJKHU HQHUJ\ WUDQVLWLRQ DQG KLJKO\ XQOLNHO\

PAGE 44

,Q DGGLWLRQ WR LQWUDPROHFXODU HIIHFWV VXFK DV WKH PHWDO VXEVWLWXHQWV DQG D[LDO OLJDQGV LQWHUPROHFXODU HIIHFWV VXFK DV DJJUHJDWLRQ FDQ VLJQLILFDQWO\ DOWHU WKH HOHFWURQLF EHKDYLRU RI SRUSK\ULQV $JJUHJDWLRQ LQ WKHVH FKURPRSKRUHV KDV EHHQ GHVFULEHG WKRURXJKO\ E\ .DVKDnV H[FLWRQ WKHRU\ 7KLV WKHRU\ ORRNV DW DJJUHJDWLRQ RQO\ IURP WKH SRLQW RI YLHZ RI RYHUODSSLQJ WUDQVLWLRQ GLSROH PRPHQWV )LJXUH f DQG QRW DV LQWHUDFWLQJ UV\VWHPV ,Q PHWDOORSRUSK\ULQV WKH WUDQVLWLRQ GLSROH PRPHQWV DUH HTXLYDOHQW GXH WR WKH V\PPHWU\ RI WKH FKURPRSKRUHf A 0\ )LJXUH 7UDQVLWLRQ GLSROH PRPHQWV LQ PHWDOORSRUSK\ULQ $JJUHJDWLRQ DFFRUGLQJ WR .DVKDfV PRGHO VSOLWV WKH H[FLWDWLRQ HQHUJ\ RI WKH PRQRPHU (rf LQWR KLJK DQG ORZ HQHUJ\ FRPSRQHQWV (TXDWLRQ GHVFULEHV WKH HQHUJ\ GHSHQGHQFH RQ DJJUHJDWLRQ E\ (s (r 's9 f ZKHUH LV WKH GLVSHUVLRQ HQHUJ\ ZKLFK LV KLJKO\ GHSHQGHQW RQ WKH FKDQJH LQ HQYLURQPHQW XSRQ DJJUHJDWLRQ DQG 9 LV WKH H[FLWRQ VSOLWWLQJ HQHUJ\

PAGE 45

:KHQ WKH FKURPRSKRUHV DUH LQWHUDFWLQJ ZLWK WKH WUDQVLWLRQ GLSROH PRPHQWV SDUDOOHO WKH H[FLWRQ HQHUJ\ FDQ EH GHVFULEHG E\ (TXDWLRQ 9 f ZKHUH 0 LV WKH WUDQVLWLRQ GLSROH PRPHQW 5 LV WKH FHQWHUWRFHQWHU GLVWDQFH 1 LV WKH QXPEHU RI FKURPRSKRUHV DQG D LV WKH DQJOH EHWZHHQ 5 DQG 0 )LJXUH f 6R LI D r 9 ZLOO EH SRVLWLYH DQG WKH H[FLWRQ VSOLWWLQJ ZLOO EH JUHDWHU DQG D UHG VKLIW ZLOO EH REVHUYHG DV WKH WUDQVLWLRQ VKLIWV WR ORZHU HQHUJ\ $ UHG VKLIW LV REVHUYHG LQ ZKDW DUH FDOOHG -DJJUHJDWHV ZKHUH ERWK 0[ DQG 0\ PDNH DQJOHV OHVV WKDQ r ZLWK WKH 5 YHFWRU ,I D r 9 ZLOO EH QHJDWLYH DQG WKH H[FLWRQ VSOLWWLQJ HQHUJ\ ZLOO EH ORZHU OHDGLQJ WR D EOXH VKLIW LQ WKH VSHFWUXP :KHQ 0[ DQG 0\ DUH ERWK JUHDWHU WKDQ r IURP 5 WKH DJJUHJDWHV DUH WHUPHG +W\SH ,I D[ DQG D\ r WKH VSHFWUDO FRPSRQHQWV ZLOO VSOLW DQG SDUW RI WKH EDQG ZLOO VKLIW UHG DQG SDUW ZLOO VKLIW EOXH WKLV VSHFWUDO EHKDYLRU LV VHHQ LQ HGJHWRHGJH W\SH DJJUHJDWHV 7KHUH FDQ EH FRPELQDWLRQV DQG YDU\LQJ GHJUHHV RI WKHVH W\SHV RI LQWHUDFWLRQV ZLWKLQ DQ DJJUHJDWHG GRPDLQ SRVVLEO\ OHDGLQJ WR FRPSOLFDWHG VSHFWUD EXW LQ JHQHUDO WKH RSWLFDO VSHFWUD HDVH LGHQWLILFDWLRQ RI HOHFWURQLF EHKDYLRU RI SRUSK\ULQ FKURPRSKRUHV )LJXUH f

PAGE 46

F )LJXUH 3RUSK\ULQ FKURPRSKRUH LQWHUDFWLRQV 7KH VTXDUH UHSUHVHQWV WKH FKURPRSKRUH DQG LWV GLVHFWLQJ D[HV $f +W\SH RU IDFHWRIDFH DJJUHJDWHV %f HGJHWR HGJH DJJUHJDWHV &f -W\SH RU KHDGWRWDLO DJJUHJDWHV 7KH WUDQVLWLRQ GLSROHV 0[ DQG 0\ DUH W\SLFDOO\ SDUDOOHO WR WKH SODQH RI WKH FKURPRSKRUH H[FHSW ZKHQ WKH QDWXUH RI WKH PHWDO LQ WKH FKURPRSKRUH FHQWHU FDXVHV D SXFNHULQJ RI WKH ULQJ 7KHUHIRUH SRODUL]HG 89YLV H[SHULPHQWV FDQ HDVLO\ LQGLFDWH RULHQWDWLRQDO FKDQJHV RI WKH FKURPRSKRUH ZLWKLQ D ILOP )LJXUH f ,QFRUSRUDWLRQ RI SRUSK\ULQV LQWR /% ILOPV LV FXUUHQWO\ RI LQWHUHVW LQ VFLHQWLILF OLWHUDWXUH 7KHVH ILOPV DUH GHVLJQHG LQ RUGHU WR SUHSDUH VHOHFWLYH JDVVHQVRUVr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n VXFK DV VWHDULF DFLG RU ZLWK ORQJ K\GURSKRELF FKDLQV

PAGE 47

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

PAGE 48

UHDFK RI WKH R[\JHQ DWRP RQ WKH PHWDO $IWHU WKH R[\JHQ KDV EHHQ VXFFHVVIXOO\ WUDQVIHUUHG WR WKH VXEVWUDWH WKH SURGXFW LV UHOHDVHG DQG WKH FDWDO\VW LV UHJHQHUDWHG 0DQJDQHVH SRUSK\ULQV DUH SUREDEO\ PRVW ZHOO NQRZQ DV HSR[LGDWLRQ DQG K\GUR[\ODWLRQ FDWDO\VWV ZKHWKHU XQGHU KHWHURJHQHRXV RU KRPRJHQHRXV FRQGLWLRQV 7KH PDQJDQHVH SRUSK\ULQ FDWDO\VWV FDQ XWLOL]H D QXPEHU RI GLIIHUHQW R[LGDQWV VXFK DV LRGRV\ODUHQHV DON\OK\GURSHUR[LGHV K\GURJHQ SHUR[LGHV DQG SHUFKORUDWHV DPRQJ RWKHUV LQ RUGHU WR DFFRPSOLVK WKH IDFLOH R[LGDWLRQ RI GHDFWLYDWHG ROHILQV DONDQHV DOFRKROV HWKHUV DQG DPLQHVn $ K\SHUYDOHQW PHWDOR[R VSHFLHV LV EHOLHYHG WR EH WKH DFWLYH LQWHUPHGLDWH LQ WKH R[LGDWLRQ SURFHVV LQ FDVHV VXFK DV GLR[\JHQ DFWLYDWLRQ RI &\WRFKURPH 3 RU LQ R[\JHQ WUDQVIHU IURP LRGRV\OEHQ]HQH SHUDFLGV RU K\SRFKORULWH R[LGDQWV 7KRXJK WKHUH LV VRPH GHEDWH RQ WKH DFWXDO PHFKDQLVP RI WKH HSR[LGDWLRQ WKHUH DUH D IHZ SRVVLEOH URXWHV )LJXUH f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b DQG SURGXFW \LHOGV JUHDWHU WKDQ b ZHUH REWDLQHG ,Q WKHVH FDWDO\VLV VWXGLHV WKH UHDFWLYH LQWHUPHGLDWH ZDV D 0Q,9f FRPSOH[

PAGE 49

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

PAGE 50

ELRPLPHWLF FDWDO\VWV KDYH EHHQ SUHSDUHG ZLWK EXON\ ULJLG JURXSV VXEVWLWXWHG RQ WKH SRUSK\ULQ FKURPRSKRUH 2QH DOWHUQDWLYH VROXWLRQ WR WKH SUREOHP RI LQWHUQDO R[LGDWLRQ RU LQWHUPROHFXODU R[LGDWLYH GHVWUXFWLRQ RI WKH SRUSK\ULQ FDWDO\VW LV LPPRELOL]DWLRQ RI WKH FKURPRSKRUH ,PPRELOL]DWLRQ LQYROYHV WHWKHULQJ WKH SRUSK\ULQ WR D VXUIDFH VXFK DV D ILOP DQ LQRUJDQLF VROLG SDUWLFOHn D SRO\PHU D PHPEUDQH RU D UHVLQ ,PPRELOL]HG SRUSK\ULQV DV ELRPLPHWLFV DQG DV KHWHURJHQHRXV FDWDO\VWV KDYH EHHQ ZHOO H[SORUHG LQ WKH SDVW VHYHUDO \HDUVnf 7HWKHULQJ RI SRUSK\ULQV WR D VROLG VXSSRUW FDQ QRW RQO\ UHGXFH RU HOLPLQDWH R[LGDWLYH GHVWUXFWLRQ RI WKH DFWLYH FDWDO\VW EXW FDQ DOVR DLG LQ WKH FDWDO\VW UHFRYHU\ DIWHU WKH UHDFWLRQ LV FRPSOHWHG +HWHURF\FOLF OLJDQGV DUH FRPPRQO\ XVHG DV WKH OLQN EHWZHHQ WKH SRUSK\ULQ DQG VXUIDFH LQ PDQ\ LPPRELOL]HG SRUSK\ULQ V\VWHPVff 8QIRUWXQDWHO\ ELQGLQJ WKH PHWDOORSRUSK\ULQ WR WKH LPLGD]ROH DOORZV OLWWOH FRQWURO RYHU WKH SRUSK\ULQ RULHQWDWLRQ LQ WKH ILOPV $GGLWLRQDOO\ LQ WKHVH FLUFXPVWDQFHV WKHUH LV QR FKHPLFDO FRQQHFWLRQ EHWZHHQ WKH SRUSK\ULQ DQG WKH VXUIDFH RWKHU WKDQ WKH OLJDQG ZKLFK OHDYHV WKH SRUSK\ULQ YXOQHUDEOH WR UHPRYDO IURP WKH VXUIDFH E\ OLJDQG GLVSODFHPHQW FKDQJLQJ WKH UHDFWLRQ FRQGLWLRQVff $Q DOWHUQDWLYH PHWKRG IRU WHWKHULQJ WKH SRUSK\ULQV WR VXUIDFHV KDV EHHQ HVWDEOLVKHG ZKLFK XVHV IRXU DON\O SKRVSKRQLF DFLG VXEVWLWXHQWV WKDW FDQ EH DWWDFKHG WR D ]LUFRQLXP SKRVSKRQDWH QHWZRUN PDNLQJ D YHU\ VWDEOH FDWDO\WLF ILOP +HWHURF\FOLF /LJDQG &RFDWDOYVWV /LJDQG DFWLYDWLRQ RI WKH SRUSK\ULQ FDWDO\VW +HWHURF\FOLF OLJDQGV DUH ZHOO GRFXPHQWHG LQ WKH OLWHUDWXUH DV DFWLYDWLQJ )H,,,f DQG 0Q,,,f SRUSK\ULQV IRU FDWDO\VLV ZLWK R[LGDQWV VXFK DV DON\O RU K\GURJHQ SHUR[LGHVff 3RUSK\ULQV

PAGE 51

LPPRELOL]HG RQ DQ LRQH[FKDQJH UHVLQ VXSSRUW VKRZHG VLJQLILFDQW LQFUHDVHV LQ FDWDO\WLF DFWLYLW\ LQ WKH SUHVHQFH RI HLWKHU LPLGD]ROH RU PHWK\OLPLGD]ROH :LWK WKH KHWHURF\FOLF OLJDQG SUHVHQW QHDUO\ TXDQWLWDWLYH FRQYHUVLRQ RI F\FORRFWHQH WR F\FORRFWHQH R[LGH ZDV DFKLHYHG UHODWLYH WR RQO\ b FRQYHUVLRQ LQ WKH DEVHQFH RI LPLGD]ROH RYHU WKH VDPH WLPH SHULRG /LNHZLVH $UDVDVLQJKDP HW DO IRXQG D WR IROG LQFUHDVH LQ WKH UDWH RI WKH UHDFWLRQ EHWZHHQ D PDQJDQHVH SRUSK\ULQ DQG DQ R[\JHQ VRXUFH FRPPRQO\ XVHG LQ ROHILQ HSR[LGDWLRQ UHDFWLRQV W%X22+ LQ WKH SUHVHQFH RI LPLGD]ROH 6LQFH WKH R[LGDWLRQ RI WKH SRUSK\ULQ DFFHOHUDWHV D UDWH LQFUHDVH VKRXOG DOVR EH REVHUYHG LQ WKH RYHUDOO HSR[LGDWLRQ UHDFWLRQ $FFRUGLQJ WR
PAGE 52

6SHFWUDO HYLGHQFH RI D[LDO OLJDQG ,P+ WR SRUSK\ULQ ELQGLQJ VKRXOG EH DSSDUHQW LQ WKH 89YLV VSHFWUD 7KH IRUPDWLRQ RI D ELVLPLGD]ROH 0Q,,,f733 &O FRPSOH[ ZDV GHPRQVWUDWHG E\ D EURDGHQLQJ VKLIW LQ WKH 6RUHW %DQG IURP QP IRU WKH SXUH SRUSK\ULQ WR QP ,QWHUHVWLQJO\ WKH HTXLOLEULXP FRQVWDQWV IRU WKH IRUPDWLRQ RI WKH PRQR DQG ELVOLJDWHG LPLGD]ROHSRUSK\ULQ FRPSOH[HV DUH VLPLODU DQG WKHLU DEVRUSWLRQ VSHFWUD DUH QHDUO\ LGHQWLFDO 7KHUHIRUH DW KLJK FRQFHQWUDWLRQV RI LPLGD]ROH LQ VROXWLRQ LW LV SRVVLEOH WKDW WKH REVHUYHG VSHFWUD DULVH IURP WKH IRUPDWLRQ RI ELVLPLGD]ROH FRPSOH[HV r +RZHYHU WKH SUHIHUUHG IRUPDWLRQ RI WKH PRQR YV ELVLPLGD]ROH FRPSOH[HV KDV FDXVHG VRPH GLVDJUHHPHQW DQG VRPH DXWKRUV FODLP WKDW HYHQ DW VDWXUDWHG FRQFHQWUDWLRQV RI LPLGD]ROH WKH SULQFLSDO FRPSRQHQW LV WKH PRQRn LPLGD]ROH RQO\ ,Q WKH 89YLV RI WKH 0QSRUSK\ULQ WKH 6RUHW %DQG RI WKH 0QSRUSK\ULQV LV WKH PRVW VHQVLWLYH WR WKH D[LDO OLJDQG 7KH FKDQJH LQ WKH 6RUHW HQHUJ\ LV GXH WR WKH FKDUJH LQGXFHG RQ WKH SRUSK\ULQ FKURPRSKRUH WKURXJK WKH PHWDO (OHFWURQGRQDWLQJ D[LDO OLJDQGV LQGXFH QHJDWLYH FKDUJH RQ WKH PDFURF\FOH VHSDUDWLQJ WKH ERQGLQJ DQG DQWLn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

PAGE 53

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fSRUSK\ULQ 3G3f DQG SDOODGLXP WULVGLFKORURSKHQ\Of WHWUDIOXRURSKHQ\O RFWDGHF\OR[\SKRVSKRQLF DFLGfSRUSK\ULQ 3G3Of KDYH EHHQ VWXGLHG DV /DQJPXLU PRQROD\HUV DQG DV ]LUFRQLXP SKRVSKRQDWH /% DQG 6$ ILOPV )LOPV ZHUH SUHSDUHG LQFRUSRUDWLQJ WKH SXUH SRUSK\ULQV DQG WKH SRUSK\ULQV PL[HG ZLWK RFWDGHF\OSKRVSKRQLF DFLG 2'3$f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f ODUJHU WKDQ WKH DUHD SHU PROHFXOH RI WKH VXEVWLWXWHG SRUSK\ULQ DQG LQ 6$ ILOPV ,Q WKHVH ILOPV WKH SRUSK\ULQ PDFURF\FOHV DUH QRQDJJUHJDWHG DQG

PAGE 54

RULHQWHG SDUDOOHO WR WKH VXUIDFH ,Q FRQWUDVW WKH PRQRSKRVSKRQLF DFLG VXEVWLWXWHG 3G3O DJJUHJDWHV XQGHU DOO RI WKH GHSRVLWLRQ FRQGLWLRQV VWXGLHG 6WDELOLW\ RI WKH 3GSRUSK\ULQ /% DQG 6$ ILOPV ZDV H[DPLQHG E\ H[SRVLQJ WKH ILOPV WR UHIOX[LQJ FKORURIRUP 89YLV DEVRUEDQFH DIWHU LPPHUVLRQ LQ FKORURIRUP FRQILUPHG FRQFOXVLRQV WKDW LQ ILOPV RI 3G3O PDQ\ RI WKH FKURPRSKRUHV DUH QRW WHWKHUHG WR WKH LQRUJDQLF QHWZRUN DQG DUH HDVLO\ UHPRYHG ZKHUHDV LQ ILOPV RI 3G3 DOO PROHFXOHV ELQG WR WKH ]LUFRQLXP SKRVSKRQDWH H[WHQGHG QHWZRUN PDNLQJ WKHVH ILOPV YHU\ UHVLOLHQW 6WXG\ RI WKH 3GSRUSK\ULQV OHG WR VLJQLILFDQW XQGHUVWDQGLQJ RI WKH EHKDYLRU RI WHWUD DQG PRQRSKRVSKRQLF DFLG SRUSK\ULQV LQ /% ILOPV &KDSWHU GHVFULEHV WKH UHVXOWV RI WKHVH VWXGLHV ZKLFK ZHUH WKH ILUVW WR VKRZ LQFRUSRUDWLRQ RI SRUSK\ULQV DW WKH H[WHULRU RI PHWDOODWWLFH FRQWDLQLQJ ILOPV 0DQJDQHVH WHWUDSKHQ\O SRUSK\ULQV DUH ZHOO NQRZQ HSR[LGDWLRQ FDWDO\VWVff DQG WKH LQFRUSRUDWLRQ RI WKHVH FDWDO\VWV LQWR ]LUFRQLXP SKRVSKRQDWH ILOPV VKRXOG LPSURYH WKHLU FDWDO\WLF HIILFLHQF\ DV ZHOO DV WKHLU VWDELOLW\ DQG UHFRYHUDELOLW\ )LOPV FRQWDLQLQJ PDQJDQHVH WHWUDNLV WHWUDIOXRURSKHQ\ORFWDGHF\OR[\SKRVSKRQLF DFLGfSRUSK\ULQ 0Q3f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f ,5 89YLV ;36 DQG VWDELOLW\ VWXGLHV FRQILUP WKH SUHVHQFH RI WKH SRUSK\ULQ 7KRURXJK FKDUDFWHUL]DWLRQ RI WKH 0Q3 FRQWDLQLQJ ILOPV LV GHVFULEHG LQ &KDSWHU

PAGE 55

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f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

PAGE 56

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

PAGE 57

7KH DPSKLSKLOHV DUH VKRZQ LQ )LJXUH DV JUD\ FLUFOHV UHSUHVHQWLQJ WKH K\GURSKLOLF KHDG JURXS DQG EODFN OLQHV UHSUHVHQWLQJ WKH K\GURSKRELF WDLOV 7KH VXESKDVH ZKLFK LV XVXDOO\ DTXHRXV PXVW EH QDQRSXUH %HFDXVH WKHUH LV VXFK D VPDOO DPRXQW RI DPSKLSKLOH SUHVHQW WKH PRQROD\HU LV H[WUHPHO\ VHQVLWLYH WR FRQWDPLQDQWV HVSHFLDOO\ OLSLGV DQG RWKHU VXUIDFWDQWV DQG LRQV IRXQG LQ VRDSV DQG WDS ZDWHU 7KH EDUULHUV FRPSUHVV WKH DPSKLSKLOHV DW D FRQVWDQW VSHHG ,Q VWXG\LQJ WKH 7 $ LVRWKHUP WKH ILOP LV FRPSUHVVHG XQWLO LW FROODSVHV )RU /% WUDQVIHUV WKH ILOP LV FRPSUHVVHG XQWLO WKH GHVLUHG WUDQVIHU SUHVVXUH LV DFKLHYHG $W WKLV SRLQW WKH PRQROD\HU LV KHOG DW FRQVWDQW SUHVVXUH IRU DSSUR[LPDWHO\ WZR PLQXWHV XQWLO WKH PRQROD\HU LV VWDELOL]HG WKHQ WKH VROLG VXEVWUDWH LV GLSSHG YHUWLFDOO\ GRZQ WKURXJK WKLV PRQROD\HU 7KH PRQROD\HUV DUH ILUVW FKDUDFWHUL]HG ZLWK ,7$ LVRWKHUPV ,Q PRGHP FRPSXWHU RSHUDWHG V\VWHPV WKH FRQFHQWUDWLRQ PJ P/nf DQG WKH PROHFXODU ZHLJKW J PROnf RU WKH FRQFHQWUDWLRQ LQ PRO /n RI WKH FRPSRXQG EHLQJ VSUHDG LV HQWHUHG LQWR WKH SURJUDP DORQJ ZLWK WKH VSUHDGLQJ VXUIDFH DUHD LQ PP )URP WKLV LQIRUPDWLRQ WKH SURJUDP FDQ FDOFXODWH WKH 00$ LQ ƒ PROHFXOH n $V WKH EDUULHUV PRYH WRJHWKHU DQG WKH VXUIDFH LV FRPSUHVVHG WKH HIIHFWLYH 00$ LV GHFUHDVHG DQG WKH VXUIDFH SUHVVXUH LQFUHDVHV 7KH SUHSDUDWLRQ RI WKH ]LUFRQLXP SKRVSKRQDWH SRUSK\ULQ ILOPV WRRN SODFH E\ D WKUHHVWHS GHSRVLWLRQ SURFHGXUH )LJXUH f!! $ JODVV VDPSOH YLDO ZDV SODFHG LQ WKH VXESKDVH LQ WKH ZHOO RI WKH WURXJK 2FWDGHF\OSKRVSKRQLF DFLG ZDV VSUHDG IURP PJ P/ &+&, VROXWLRQV DQG FRPSUHVVHG DW PP PLQ RQ WKH ZDWHU VXUIDFH $W P1 Pn WKH VXEVWUDWH ZDV GLSSHG GRZQ WKURXJK WKH PRQROD\HU VXUIDFH DQG LQWR WKH VDPSOH YLDO DW PP PLQ WUDQVIHUULQJ WKH 2'3$ WHPSODWH OD\HU 7KH VXEVWUDWH DQG WKH YLDO ZHUH WKHQ UHPRYHG IURP WKH WURXJK DQG DQ DPRXQW RI ]LUFRQ\O FKORULGH ZDV DGGHG WR WKH YLDO WR PDNH WKH VROXWLRQ FD [ 0 LQ =+ $IWHU PLQ LQ WKH

PAGE 58

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n 7R IRUP WKH FDSSLQJ OD\HU E\ VHOIDVVHPEO\ WKH K\GURSKLOLF VXUIDFH ZDV VXEPHUJHG LQ D VROXWLRQ RI WKH GHVLUHG PROHFXOHV DW DERXW 2n 0 LQ DQ DSSURSULDWH VROYHQW XVXDOO\ (W2++ f 7KH FDSSLQJ OD\HU ZDV WKHQ DOORZHG WR VHOIDVVHPEOH 0DWHULDOV DQG 0HWKRGV 0DWHULDOV XVHG WR SUHSDUH WKH SRUSK\ULQ FRQWDLQLQJ ILOPV LQFOXGHG RFWDGHF\OSKRVSKRQLF DFLG 2'3$f ]LUFRQ\O FKORULGH =Q&O+f DQG WKH SRUSK\ULQV WKHPVHOYHV 7KH SRUSK\ULQV ZHUH SURYLGHG E\ %UXQR %XMROL )DEULFH 2GREHO .DULQH /H&ODLU DQG /DXUHQW &DPXV IURP WKH /DERUDWRLUH GH 6\QWKHVH 2UJDQLTXH DW WKH )DFXOWH GHV 6FLHQFHV HW GHV 7HFKQLTXHV GH 1DQWHV LQ 1DQWHV )UDQFH 2'3$ ZDV XVHG DV SXUFKDVHG IURP $OID $HVDU :DUG +LOO 0$f =LUFRQ\O FKORULGH b ZDV XVHG DV VXSSOLHG IURP $OGULFK 0LOZDXNHH :,f 2FWDGHF\OWULFKORURVLODQH 276f b XVHG WR VLODQL]H DQG KHQFH K\GURSKRELFL]H WKH VXEVWUDWHV ZDV DOVR XVHG DV SXUFKDVHG IURP $OGULFK $P\OHQH VWDELOL]HG +3/& JUDGH &+&OM ZDV XVHG DV D VSUHDGLQJ VROYHQW DQG ZDV XVHG DV UHFHLYHG IURP $FURV 3LWWVEXUJK 3$f DQG )LVKHU 6FLHQWLILF 3LWWVEXUJK 3$f $ .69 V\VWHP 6WUDWIRUG &7f ZDV XVHG LQ FRPELQDWLRQ ZLWK D KRPHPDGH GRXEOH EDUULHU 7HIORQ WURXJK IRU WKH /DQJPXLU PRQROD\HU VWXGLHV DQG /% ILOP SUHSDUDWLRQ

PAGE 59

67(3 67(3 )LJXUH 6FKHPDWLF RI WKH WKUHHVWHS GHSRVLWLRQ SURFHVV XVHG IRU ]LUFRQLXP SKRVSKRQDWH ILOPV

PAGE 60

7KH VXUIDFH DUHD RI WKH WURXJK ZDV FP FP [ FPf $ SODWLQXP RU ILOWHU SDSHU :LOKHOP\ SODWH VXVSHQGHG IURP D .69 PLFUREDODQFH PHDVXUHG WKH VXUIDFH SUHVVXUH 6XESKDVHV ZHUH XVXDOO\ SXUH ZDWHU ZLWK D UHVLVWLYLW\ RI 04 FPB SURGXFHG IURP D %DPVWHDG 1$12SXUH %RVWRQ 0$f SXULILFDWLRQ V\VWHP 7KH ILOPV ZHUH WUDQVIHUUHG IURP WKH DTXHRXV VXUIDFH RQWR VROLG VXSSRUWV *ODVV PLFURVFRSH VOLGHV DQG JODVV FRYHUVOLSV ZHUH SXUFKDVHG IURP )LVFKHU 3LWWVEXUJK 3$f DQG ZHUH XVHG DV VXEVWUDWHV IRU 89YLV DQG FDWDO\VLV VWXGLHV 6LQJOH FU\VWDO VLOLFRQ ZDIHUV f ZHUH SXUFKDVHG IURP 6HPLFRQGXFWRU 3URFHVVLQJ &RPSDQ\ %RVWRQ 0$f DQG FXW XVLQJ D GLDPRQG JODVV FXWWHU WR PP [ PP [ PP IRU ;36 VWXGLHV 7KHVH VXEVWUDWHV ZHUH FOHDQHG XVLQJ SLUDQKD HWFK ZKLFK LV +6 b + D QHZ K\GURSKLOLF VXUIDFH ZDV SUHSDUHG E\ WKH 5&$ SURFHGXUH ZKLFK LQYROYHG ILUVW KHDWLQJ LQ D VROXWLRQ RI ZDWHU b + DQG 1+2+ DQG VHFRQG KHDWLQJ LQ D VROXWLRQ RI ZDWHU b + DQG +& 7KHQ WKH VXEVWUDWHV ZHUH VRQLFDWHG IRU PLQXWHV HDFK LQ PHWKDQRO E\ YROXPH PHWKDQRO FKORURIRUP DQG FKORURIRUP 7KH VXEVWUDWHV ZHUH WKHQ VRQLFDWHG LQ D b RFWDGHF\OWULFKORURVLODQH 276f VROXWLRQ LQ KH[DGHFDQH DQG &+& IRU WZR KRXUV )LQDOO\ WKH VXEVWUDWHV ZHUH VRQLFDWHG IRU PLQXWHV HDFK LQ &+& E\ YROXPH &+2+ &+& DQG &+M2+} &KDUDFWHUL]DWLRQ 89YLV 7UDQVPLWWDQFH 89YLVLEOH H[SHULPHQWV ZHUH SHUIRUPHG RQ D &DU\ VSHFWURSKRWRPHWHU E\ 9DUDQ ZLWK DQ DYHUDJH UHVROXWLRQ RI QP 3RUSK\ULQ VROXWLRQV ZHUH VWXGLHG E\ 89YLV LQ (W2+ + &+& DQG &+& VROYHQWV 7KH EHKDYLRU RI WKH SRUSK\ULQ ZLWK GLIIHUHQW SRWHQWLDO OLJDQGV ZDV LQYHVWLJDWHG E\ PL[LQJ WKH SRUSK\ULQ VROXWLRQ ZLWK HWK\OSKRVSKRQLF DFLG WEXW\O DPPRQLXP KDOLGHV FKORULGH

PAGE 61

DQG EURPLGHf $OGULFKf DQG LPLGD]ROH ZLWK QR DON\O VXEVWLWXHQWV ,P+f .RGDNf $ FP [ FP [ FP TXDUW] FXYHWWH KHOG WKH VDPSOH DQG WKH EDFNJURXQG XVLQJ WKH FRUUHVSRQGLQJ SXUH VROYHQW ZDV VXEWUDFWHG $ 7HIORQ VXEVWUDWH KROGHU ZLWK JURRYHV FXW DW r WR RQH DQRWKHU ZDV XVHG WR REWDLQ VDPSOLQJ DW r EHDP QRUPDO WR WKH VXEVWUDWHf DQG r LQFLGHQFH WR WKH VXEVWUDWH VXUIDFH $ SODQH YLVLEOH SRODUL]HU ZDV XVHG WR VHOHFW V DQG SSRODUL]HG OLJKW 5HIOHFWDQFH 89YLV H[SHULPHQWV ZHUH SHUIRUPHG RQ D .69 PLQLWURXJK XVLQJ DQ 2ULHO VSHFWURSKRWRPHWHU DQG D ILOWHU ZLWK D UDQJH IURP QP ;UD\ 3KRWRHOHFWURQ 6SHFWURVFRS\ ;UD\ SKRWRHOHFWURQ VSHFWURVFRS\ ;36f ZDV SHUIRUPHG RQ D 3HUNLQ(OPHU 3+, 6HULHV VSHFWURPHWHU XVLQJ WKH 0J .D OLQH VRXUFH DW H9 7KH LQVWUXPHQWDO UHVROXWLRQ ZDV H9 ZLWK DQRGH YROWDJH DQG SRZHU VHWWLQJV RI N9 DQG : UHVSHFWLYHO\ 7KH RSHUDWLQJ SUHVVXUH ZDV DURXQG [ f DWP 6XUYH\ VFDQV ZHUH SHUIRUPHG DW D r WDNHRII DQJOH ZLWK D SDVV HQHUJ\ RI H9 'XULQJ PXOWLSOH[ VFDQV VFDQV ZHUH UXQ DW HDFK SHDN RYHU D H9 UDQJH ZLWK D SDVV HQHUJ\ RI H9 ;UDY 'LIIUDFWLRQ ,Q RUGHU WR REWDLQ ORZ DQJOH ;UD\ GLIIUDFWLRQ ;5'f SDWWHUQV PXOWLOD\HU ILOPV ZHUH WUDQVIHUUHG RQWR D K\GURSKRELF JODVV VOLGH 7KH GLIIUDFWLRQ SDWWHUQV ZHUH REWDLQHG XVLQJ D 3KLOOLSV $3' ;UD\ SRZGHU GLIIUDFWRPHWHU ZLWK WKH &X.D OLQH ; ƒ DV WKH VRXUFH IRU ILOPV UDQJLQJ IURP WR ELOD\HUV $WWHQXDWHG 7RWDO 5HIOHFWDQFH ,QIUDUHG $WWHQXDWHG WRWDO UHIOHFWDQFH LQIUDUHG VSHFWURVFRS\ ZDV SHUIRUPHG RQ D 0DWWVRQ ,QVWUXPHQWV 0DGLVRQ :,f 5HVHDUFK 6HULHV )7,5 VSHFWURPHWHU HTXLSSHG ZLWK D GHXWHUDWHG WULJO\FHULGH VXOILGH GHWHFWRU DQG D +DUULFN 2VVLQLQJ 1
PAGE 62

3RUSK\ULQ )LOPV 3DOODGLXP 3RUSK\ULQ )LOPV 7KH SDOODGLXP SRUSK\ULQV VWXGLHG ZHUH SDOODGLXP WHWUDNLV WHWUDIOXRURSKHQ\ORFWDGHF\OR[\SKRVSKRQLF DFLGfSRUSK\ULQ 3G3f DQG SDOODGLXP WULVGLFKORURSKHQ\Of WHWUDIOXRURSKHQ\O RFWDGHF\OR[\SKRVSKRQLF DFLGfSRUSK\ULQ 3G3Of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f WR 2'3$ VWXGLHG LQFOXGHG DQG UHVSHFWLYHO\ 7KH FUHHS RI WKH SXUH SDOODGLXPSRUSK\ULQ /DQJPXLU PRQROD\HUV ZDV VWXGLHG DW KLJK DQG ORZ SUHVVXUHV RYHU PLQ RU VOLJKWO\ ORQJHU WKDQ WKH WLPH RI RQH GHSRVLWLRQ $W D FRQVWDQW SUHVVXUH RI P1 QU WKH DUHD FKDQJHG E\ b DQG b IRU 3G3 DQG 3G3 UHVSHFWLYHO\ $W ORZ SUHVVXUH P1 QUf WKH FKDQJH LQ DUHD ZDV b DQG b IRU 3G3 DQG 3G3O UHVSHFWLYHO\ 7KH LQVWDELOLW\ LQ WKH PRQROD\HUV OHG WR D QHFHVVDU\ FRUUHFWLRQ LQ WKH WUDQVIHU UDWLRV 7KH FRUUHFWHG WUDQVIHU UDWLRV IRU WKH SXUH 3G3 ZHUH DW KLJK SUHVVXUHV DQG DW ORZ SUHVVXUHV )RU WKH SXUH 3G3O WKH FRUUHFWHG WUDQVIHU UDWLRV ZHUH DQG IRU KLJK

PAGE 63

SUHVVXUH DQG ORZ SUHVVXUH WUDQVIHUV UHVSHFWLYHO\ 7KH WUDQVIHU UDWLRV RI WKH SRUSK\ULQ ILOPV PL[HG ZLWK 2'3$ FRQVLVWHQWO\ VKRZHG XQFRUUHFWHG WUDQVIHU UDWLRV QHDU XQLW\ 0RQROD\HUV RI 3G3 DQG 3G3 ZHUH DOVR VWXGLHG RQ ERWK KHDWHG DQG EDVLF VXESKDVHV 7R KHDW WKH WURXJK DQ ,VRWHPS 5HIULJHUDWLQJ &LUFXODWLQJ 0RGHO )LVKHU 6FLHQWLILFf SXPS ZLWK D ZDWHUHWK\OHQH JO\FRO EDWK ZDV XVHG 7KH WHPSHUDWXUH RI WKH VXESKDVH ZDV PRQLWRUHG XVLQJ D .69 WKHUPRVHQVRU $ 0 .2+ VROXWLRQ ZDV DGGHG WR WKH VXESKDVH WR DGMXVW WKH S+ WR WKH GHVLUHG YDOXH 3G3 ILOPV ZHUH DOVR VWXGLHG E\ VHOIDVVHPEO\ 7KH 6$ VROXWLRQ ZDV SUHSDUHG E\ GLOXWLQJ P/ RI D PJ P/n VROXWLRQ RI 3G3 LQ &+& WR P/ ZLWK D (W2++ PL[WXUH 7KH ILOP ZDV DOORZHG WR 6$ IRU DSSUR[LPDWHO\ KRXUV EHIRUH VWXG\LQJ E\ 89YLV 0DQJDQHVH 3RUSK\ULQ )LOPV 0DQJDQHVH WHWUDNLVWHWUDIOXRURSKHQ\O RFWDGHF\OR[\SKRVSKRQLF DFLGfSRUSK\ULQ 0Q3f DQG D PRGHO SRUSK\ULQ PDQJDQHVH WHWUDNLV SHQWDIOXRURSKHQ\OfSRUSK\ULQ 0Q32f ZHUH SUHSDUHG E\ WKH %XMROL JURXS $JDLQ 2'3$ ZDV XVHG IRU WKH WHPSODWH OD\HUV ]LUFRQ\O FKORULGH ZDV XVHG WR SUHSDUH WKH ]LUFRQLXP QHWZRUN DQG &+& ZDV XVHG DV WKH VSUHDGLQJ VROYHQW $OVR W EXW\ODPPRQLXP FKORULGH L%X1+ &Onf $OGULFKf ZDV XVHG DV D FKORULGH VRXUFH IRU 6$ GHSRVLWHG ILOPV 1D&O $FURVf ZDV XVHG DV WKH FKORULGH VRXUFH IRU /% WUDQVIHUUHG ILOPV 7R IRUP WKH 0Q3 PRQROD\HUV D PJ P/n VROXWLRQ ZDV SUHSDUHG LQ &+& RIWHQ LQ RUGHU WR GLVVROYH WKH SRUSK\ULQV XS WR b HWKDQRO ZDV DGGHG DQG WKH VROXWLRQ ZDV VRQLFDWHG IRU DERXW DQ KRXUf $Q DSSURSULDWH YROXPH RI VROXWLRQ ZDV VSUHDG RQ WKH DTXHRXV VXUIDFH LQ RUGHU WR UHDFK DQG KROG WKH GHVLUHG WUDQVIHU SUHVVXUH

PAGE 64

WKURXJKRXW WKH GHSRVLWLRQ $ YDULHW\ RI VXUIDFH SUHVVXUHV ZHUH XVHG IRU WUDQVIHU DQG ZLOO EH GHVFULEHG LQ PRUH GHWDLO LQ &KDSWHU 7R SUHSDUH 6$ 0QSRUSK\ULQ ILOPV P/ RI D PJ P/n 0Q3 VROXWLRQ LQ (W2+ ZDV GLOXWHG WR P/ ZLWK D (W2++ PL[WXUH LQ D P/ YLDO $OWHUQDWLYHO\ D PJ P/n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fV D[LDO SRVLWLRQ D 6$ VROXWLRQ FRQWDLQLQJ DSSUR[LPDWHO\ 0 W%X1+ &On DORQJ ZLWK WKH SRUSK\ULQ LQ (W2++ ZDV SUHSDUHG 7KH ]LUFRQDWHG 2'3$ WHPSODWH ZDV VXEPHUJHG LQ WKLV VROXWLRQ IRU KU $OWHUQDWLYHO\ FKORULGH LRQV ZHUH LQFRUSRUDWHG LQWR WKH DTXHRXV VXESKDVH XVHG IRU /% WUDQVIHU RI WKH 0Q3 PRQROD\HUV XVLQJ 1D&O DW 0 DQG JUHDWHU FRQFHQWUDWLRQV )URP 89YLV UHVXOWV RI WKH 0Q3 DQG 0Q32 ZLWK HWK\OSKRVSKRQLF DFLG LW DSSHDUHG WKDW WKH SKRVSKRQLF DFLG PLJKW FDXVH WKH 0Q,,,fSRUSK\ULQ WR JR WKURXJK D VSLQ VWDWH FURVVRYHU IURP KLJKVSLQ WR ORZVSLQ 0Q,,,f ,Q RUGHU WR H[DPLQH WKLV PDJQHWLF FKDQJH WKH (YDQfV 105 PHWKRG ZDV XVHGf $ VROXWLRQ RI b W

PAGE 65

EXWDQRO LQ &'& ZDV LQMHFWHG LQWR D VPDOO FDSLOODU\ WXEH XVLQJ D ORQJ V\ULQJH QHHGOH 7KH GHSWK RI WKH VROXWLRQ LQ WKH FDSLOODU\ WXEH UHDFKHG DSSUR[LPDWHO\ f 7ZR VWDQGDUG 105 WXEHV ZHUH WKHQ ILOOHG WR DSSUR[LPDWHO\ f ZLWK VDPSOH VROXWLRQ 7KH ILUVW ZDV ILOOHG ZLWK SXUH 0Q32 J SPROf GLVVROYHG LQ WKH b W EXWDQRO&'&O VROXWLRQ 7KH VHFRQG ZDV ILOOHG ZLWK 0Q32 J SPROf DQG HWK\OSKRVSKRQLF DFLG J SPROf 7KH UHIHUHQFH VROXWLRQ LQ WKH FDSLOODU\ ZDV LQVHUWHG LQWR WKH SRUSK\ULQ FRQWDLQLQJ 105 VDPSOH DQG WKH PDJQHWLF VXVFHSWLELOLW\ RI WKH VROXWH [J FP Jnf LQGXFHG E\ WKH PDJQHWLF SRUSK\ULQ ZDV DSSUR[LPDWHG E\ Y $ J $XIP f ZKHUH $I LV WKH GLDPDJQHWLF IUHTXHQF\ VKLIW I LV WKH VSHFWURPHWHU IUHTXHQF\ DQG P LV WKH PDVV RI VXEVWDQFH SHU P/ RI VROXWLRQ &RPSDUHG WR OLWHUDWXUH YDOXHV WKH GLIIHUHQFHV LQ WKH [J RI 0Q32 ZLWK DQG ZLWKRXW HWK\OSKRVSKRQLF DFLG GLG QRW FRUUHVSRQG WR D VSLQ VWDWH FKDQJH LQ WKH 0Q,,,f 0DQJDQHVH 3RUSKYULQ,PLGD]ROH 0L[HG )LOPV 7KH JHQHUDO PHWKRG XVHG WR SUHSDUH 0Q3LPLGD]ROH ILOPV LQ WKLV VWXG\ LQYROYHG WKH LQLWLDO IRUPDWLRQ RI D ]LUFRQDWHG RFWDGHF\OSKRVSKRQLF DFLG 2'3$f WHPSODWH DV EHIRUH 2QWR WKLV WHPSODWH D ILOP RI HLWKHU SXUH LPLGD]ROH RFWDGHF\OSKRVSKRQLF DFLG ,P2'3$f ZKLFK ZDV SUHSDUHG E\ WKH %XMROL JURXS RU D PL[WXUH RI ,P2'3$ DQG 0Q3 FRXOG EH IRUPHG 7KH ]LUFRQLXP SKRVSKRQDWH QHWZRUN SURYLGHG D PHDQV IRU ORFNLQJ WKH SRUSK\ULQ DQG WKH LPLGD]ROH LQWR WKH ILOPV UHVXOWLQJ LQ ILOPV WKDW ZHUH VWDEOH WRZDUG WKH FRQGLWLRQV XVHG IRU WKH FDWDO\VLV

PAGE 66

UHDFWLRQV (YHQ XQGHU UHODWLYHO\ KDUVK FRQGLWLRQV VXFK DV HOHYDWHG WHPSHUDWXUHV RU UDSLG VROYHQW IORZ WKH SRUSK\ULQV ILOPV DSSHDUHG WR EH VWDEOH $GGLWLRQDOO\ WKH ]LUFRQLXP SKRVSKRQDWH QHWZRUN PDGH SUHSDUDWLRQ RI WKH 0Q3LPLGD]ROH ILOPV SRVVLEOH E\ D ZLGH YDULHW\ RI PHFKDQLVPV 0Q3 DQG ,P2'3$ FRXOG EH LQFRUSRUDWHG LQWR ERWK /% DQG 6$ ILOPV ,Q RUGHU WR DFFRPPRGDWH ,P2'3$ LQWR /% ILOPV WZR W\SHV RI VSUHDGLQJ VROXWLRQV ZHUH XVHG f ,P2'3$ PL[HG ZLWK D VWDELOL]LQJ DJHQW VXFK DV KH[DGHF\OSKRVSKRQLF DFLG +'3$f RU f ,P2'3$ PL[HG ZLWK WKH 0Q3 DPSKLSKLOH $ORQH WKH ,P2'3$ GLG QRW IRUP VXIILFLHQWO\ VWDEOH PRQROD\HUV IRU WUDQVIHU 7KH SRUSK\ULQ 0Q3 ZDV VXEVWLWXWHG LQWR WKH ILOPV RI SXUH ,P2'3$ RU ,P2'3$+'3$ IURP DQ (W2++ VROXWLRQ $OWHUQDWLYHO\ WKH 0Q3 ILOP ZDV WUDQVIHUUHG E\ WKH /% WHFKQLTXH DQG WKHQ WKH ,P2'3$ ZDV VXEVWLWXWHG LQWR WKHVH ILOPV )LUVW LQ WKH FDVH RI WKH PL[HG b ,P2'3$b +'3$ ILOPV S/ RI D VROXWLRQ ZLWK D ZHLJKWHG DYHUDJH FRQFHQWUDWLRQ RI PJP/ DQG D ZHLJKWHG DYHUDJH PROHFXODU ZHLJKW RI PJ PPROn ZDV VSUHDG RQ WKH ZDWHU VXUIDFH DQG FRPSUHVVHG WR P1 Pn 7KH ILOP ZDV WUDQVIHUUHG DW PP PLQn RQ WKH XSVWURNH FRPSOHWLQJ WKH ]LUFRQLXP QHWZRUN )LOPV PDGH LQ WKLV ZD\ ZHUH DEEUHYLDWHG 2'3$=Ub ,P2'3$ 7KHVH ILOPV ZHUH WKHQ SODFHG LQ D VROXWLRQ RI WKH 0Q3 DW FDn 0 LQ (W2++ DQG WKH SRUSK\ULQ SKRVSKRQLF DFLGV ZHUH DOORZHG WR VXEVWLWXWH LQWR WKH GHIHFW RU YDFDQW VLWHV LQ WKH ILOP IRU KU 7UDQVPLVVLRQ 89YLV RI WKHVH ILOPV FRQILUPV WKH DELOLW\ WR LQFOXGH WKH SRUSK\ULQV E\ WKLV PHWKRG DQG WKH UHVXOWLQJ ILOPV ZHUH FDOOHG 2'3$=Ub ,P2'3$ 6$ 0Q3 )LOPV FRQWDLQLQJ ERWK WKH 0Q3 DQG WKH ,P2'3$ WUDQVIHUUHG E\ WKH /% WHFKQLTXH IURP D PL[HG PRQROD\HU ZHUH DOVR SUHSDUHG $ PL[WXUH RI 0Q3,P2'3$ UHVSHFWLYHO\ ZDV GLVVROYHG LQ &+& ZLWK D ZHLJKWHG FRQFHQWUDWLRQ DQG 0: RI PJP/ DQG UHVSHFWLYHO\ S/ RI WKLV VROXWLRQ ZDV

PAGE 67

VSUHDG DQG WUDQVIHUUHG DW PP PLQn RQ WKH XSVWURNH IRUPLQJ WKH 2'3$=U 0Q3,P2'3$ ILOPV )RU WKH VHOIDVVHPEO\ RI WKH LPLGD]ROH RQWR D ]LUFRQDWHG 2'3$ WHPSODWH P/ RI D PJ P/n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f DV WKH R[LGDQW 3K,2 ZDV V\QWKHVL]HG IURP WKH GLDFHWDWH SUHFXUVRU XVLQJ 1D2+ ,RGREHQ]HQH GLDFHWDWH J PPROf ZDV SODFHG LQ DQ (UOHQPH\HU IODVN P/ RI 1 1D2+ ZDV DGGHG ZLWK VWLUULQJ RYHU PLQ 7KH PL[WXUH ZDV VWLUUHG IRU PLQ DQG OHIW WR VLW XQFRYHUHG PLQ P/ GHLRQL]HG + ZDV DGGHG ZLWK VWLUULQJ DQG WKH \HOORZ VROLG ZDV ILOWHUHG XVLQJ D %XFKQHU IXQQHO

PAGE 68

7KH VROLG ZDV FROOHFWHG DQG ZDVKHG ZLWK DQRWKHU P/ DOLTXRW RI + 7KH VROLG ZDV ILOWHUHG DJDLQ DQG ZDVKHG ZLWK &+& WLPHV LQ D EHDNHU DQG ILOWHUHG 7KH VROLG ZDV GULHG LQ D YDFXXP GHVLFFDWRU 7KH SURGXFWfV PHOWLQJ SRLQW FRUUHVSRQGHG ZHOO WR WKH OLWHUDWXUH YDOXH RI r & ,RGRPHWULF WLWUDWLRQ LQYROYLQJ FRQYHUWLQJ WKH 3K,2 SURGXFW WR 3KL DQG ZLWK +, DQG WLWUDWLQJ ZLWK VRGLXP WKLRVXOIDWH JDYH D SXULW\ RI b 3K,2 PJ SPROf ZDV GLOXWHG LQ P/ &+& 7KH 3K,2 FRPSRXQG ZDV RQO\ VOLJKWO\ VROXEOH LQ &+& VR LW ZDV GLOXWHG DQG WKHQ VRQLFDWHG IRU DW OHDVW PLQ $IWHU VRQLFDWLQJ DQ DPRXQW RI WKH F\FORRFWHQH ZDV DGGHG DQG WKH PL[WXUH ZDV VWLUUHG IRU DERXW PLQ 'HFDQH S/ SPRO RU S/ SPROf WKH LQWHUQDO VWDQGDUG ZDV DOVR DGGHG ZLWK VWLUULQJ OP/ VDPSOHV RI WKLV PL[WXUH ZHUH XVHG IRU ERWK D EODQN UXQ DQG D KRPRJHQHRXV UXQ ,Q DOO KRPRJHQHRXV H[SHULPHQWV S/ RI D P0 VROXWLRQ RI 0Q32 ZDV DGGHG WR WKH EODQN VROXWLRQ WR LQYHVWLJDWH WKH HSR[LGH \LHOGV ZLWK WKH SRUSK\ULQ LQ VROXWLRQ )LJXUH 6FKHPDWLF RI FDWDO\VLV FHOO VLGH YLHZ

PAGE 69

$SSUR[LPDWHO\ P/ RI WKH DERYH R[LGDQWVXEVWUDWH VROXWLRQ ZDV WUDQVIHUUHG LQWR D VPDOO (UOHQPH\HU IODVN DQG IURP WKHUH ORDGHG LQWR WKH IORZ FHOOV XVHG IRU VWXG\LQJ FDWDO\VLV ZLWK WKH ILOPV $OVR EODQNV DQG KRPRJHQHRXV VROXWLRQV ZHUH ORDGHG LQWR FHOOV FRQWDLQLQJ EODQN ILOPV QR FDWDO\VWf IRU VWXG\LQJ SURGXFW \LHOGV DIIHFWHG E\ WKH IORZ FHOO 9LWRQ FHOO %RWWRP SODWH *URRYH ZLWK 9LWRQ RULQJ 9LWRQ FHOO 7RS SODWH )LJXUH 6FKHPDWLF RI FDWDO\VLV FHOO WRS YLHZ 7KH IORZ FHOOV ZHUH EXLOW E\ WKH 8QLYHUVLW\ RI )ORULGD PDFKLQH VKRS 7KH FHOO ZDV PDGH IURP WZR EORFNV RI 'HOULQ LQWR ZKLFK ZDV FDUYHG D FHOO ZLWK GLPHQVLRQV f [ f [ f ,QOHW DQG RXWOHW WXEHV ZHUH SODFH DW WKH FHOO HGJHV 2QH HQG RI D f OHQJWK RI f ,' 9LWRQ WXELQJ &ROH3DUPHU 9HUQRQ +LOOV ,/f ZDV FRQQHFWHG WR WKH LQOHW SRUW DQG WKH RWKHU HQG ZDV VXEPHUJHG LQ WKH UHDFWLRQ VROXWLRQ $ &ROH3DUPHU 0DVWHUIOH[ SHULVWDOWLF SXPS PRGHO f USPf ZLWK DQ HDV\ORDG KHDG ZDV XVHG WR LQWURGXFH WKH VROXWLRQ LQWR WKH FHOO WKHQ WKH RSHQ HQG RI WKH 9LWRQ WXELQJ ZDV UHPRYHG IURP WKH VROXWLRQ DQG FRQQHFWHG WR WKH RXWOHW SRUW RI WKH FHOO 7KH VROXWLRQ ZDV FLUFXODWHG DURXQG WKH ILOP XVLQJ WKH SHULVWDOWLF SXPS

PAGE 70

7KH UHDFWLRQ SURGXFWV ZHUH VWXGLHG E\ *& 7KH *& LQVWUXPHQW ZDV D 6KLPDG]X *&$ &ROXPELD 0'f ZLWK D K\GURJHQ IODPH LRQL]DWLRQ GHWHFWRU $ S/ SRUWLRQ RI WKH UHDFWLRQ VROXWLRQ ZDV LQMHFWHG RQWR WKH P PP ,' 57; FROXPQ &URVVERQG b GLSKHQ\Ob GLPHWK\O SRO\VLOR[DQHf 7KH FROXPQ ZDV KHOG DW r & IRU PLQ DQG WKHQ UDPSHG DW r & PLQn IRU PLQ 6HQVLWLYLW\ IDFWRUV Nf ZHUH GHWHUPLQHG XVLQJ GHFDQH DQG RGLFKORUREHQ]HQH DV WKH LQWHUQDO VWDQGDUGV $ VHULHV RI UXQV ZHUH SHUIRUPHG IRU ERWK WKH F\FORRFWHQH &\2f DQG WKH F\FORRFWHQH R[LGH &\22f VWDQGDUGV (TXDWLRQ ZDV XVHG WR FDOFXODWH fNf IURP WKH *& WUDFH DUHDV RI WKH VWDQGDUG $Vf DQG WKH SURGXFW $&\f DQG WKH NQRZQ VDPSOH ZHLJKWV Z&\ DQG ZVf n‘&\22 :&\L;fA6 ZV$\RR f $IWHU DQ DYHUDJH N YDOXH ZDV REWDLQHG IRU WKH &\2 DQG &\22 WKH FDWDO\VLV \LHOGV ZHUH GHWHUPLQHG IURP WKH UHDFWLRQ PL[WXUH XVLQJ (TXDWLRQ :&\22 a f&\22 :6$& n\82 $V f %HFDXVH WKH 3K,2 R[LGDQW ZDV UDWKHU LQVROXEOH D VHULHV RI P/ DOLTXRWV RI D J / VROXWLRQ RI 3K,2 LQ &+& ZHUH GULHG DQG ZHLJKHG 7KH ILQDO ZHLJKWV ZHUH PJ s b DVVXULQJ XV WKDW WKH DPRXQW RI R[LGDQW LQ HDFK UHDFWLRQ ZDV DSSUR[LPDWHO\ WKH VDPH ,Q RUGHU WR FRPSDUH QHDUO\ WKH VDPH FRQFHQWUDWLRQV RI FDWDO\VW LQ ERWK WKH KRPRJHQHRXV DQG KHWHURJHQHRXV FDVHV WKH FRQFHQWUDWLRQ RI SRUSK\ULQV LQ WKH ILOPV

PAGE 71

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f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

PAGE 72

&+$37(5 3$//$',80 3253+<5,1 &217$,1,1* =,5&21,80 3+263+21$7( /$1*08,5%/2'*(77 ),/06 %DFNJURXQG RQ 3DOODGLXP 3RUSK\ULQ )LOPV /DQJPXLU PRQROD\HUV DQG /% ILOPV RI WKH GHULYDWL]HG SDOODGLXP WHWUDSKHQ\O SRUSK\ULQ PROHFXOHV SDOODGLXP WHWUDNLVWHWUDIOXRURSKHQ\O RFWDGHF\OR[\SKRVSKRQLF DFLGfSRUSK\ULQ DQG SDOODGLXP WULV GLFKORURSKHQ\Of WHWUDIOXRURSKHQ\ORFWDGHF\OR[\SKRVSKRQLF DFLGf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f ZHUH GHVLJQHG WR LQYHVWLJDWH ZKHWKHU SRUSK\ULQV FDQ EH LQFRUSRUDWHG LQWR PHWDO SKRVSKRQDWH /% ILOPV $OVR EHFDXVH RI WKHLU ZHOOXQGHUVWRRG VSHFWURVFRSLF EHKDYLRU WKH 3G3 PROHFXOHV ZHUH XVHG WR VWXG\ KRZ WKH RULHQWDWLRQ DQG DJJUHJDWLRQ RI WKH SRUSK\ULQ FDQ EH FRQWUROOHG LQ WKH GHSRVLWHG ILOPV

PAGE 73

5 &+f3+ 5 $ % )LJXUH 6WUXFWXUHV RI $f 3G3 DQG %f 3G3O 3DOODGLXP SRO\KDORJHQDWHG SRUSK\ULQV ZHUH FKRVHQ EDVHG RQ WKH IROORZLQJ FRQVLGHUDWLRQV )LUVW SDOODGLXP SRUSK\ULQV DUH QRW GHPHWDOODWHG LQ DFLGLF FRQGLWLRQV DQG WKHLU GLDPDJQHWLF FKDUDFWHU PDNHV IROORZLQJ WKH V\QWKHVLV ZLWK 105 VSHFWURVFRS\ SRVVLEOH 6HFRQG PDQJDQHVH DQG LURQ SRO\KDORJHQDWHG SRUSK\ULQV DUH ZHOONQRZQ FDWDO\VWV IRU WKH R[LGDWLRQ RI K\GURFDUERQV WKHUHIRUH LI SDOODGLXP LV UHSODFHG E\ RQH RI WKHVH PHWDOV WKH ILOPV FDQ EH XVHG IRU FDWDO\WLF DSSOLFDWLRQV 7KLUG SHQWDIOXRURSKHQ\O VXEVWLWXHQWV RQ SRUSK\ULQV DOORZ VWUDLJKWIRUZDUG IXQFWLRQDOL]DWLRQ RI WKLV OLJDQG E\ DURPDWLF QXFOHRSKLOLF GLVSODFHPHQW ZLWK DQ DOFRKRO ,Q DGGLWLRQ WKH HWKHU ERQGV DUH PRUH VWDEOH WRZDUG K\GURO\VLV DQG OHVV K\GURSKLOLF WKDQ WKH HVWHU RU DPLGH OLQNDJHV XVXDOO\ XVHG WR WHWKHU DON\O FKDLQV RQ SRUSK\ULQV +LJK K\GURSKRELFLW\ RI WKH OLQNDJH LV D UHTXLUHPHQW EHFDXVH FRPSHWLWLRQ ZLWK WKH SRODU SKRVSKRQLF DFLG KHDGJURXS VKRXOG EH DYRLGHG GXULQJ WKH /% ILOP SUHSDUDWLRQ

PAGE 74

/% ILOPV RI 3G3 DQG 3G3O ZHUH IRUPHG LQFRUSRUDWLQJ D ]LUFRQLXP SKRVSKRQDWH QHWZRUN 7KH VWURQJ WHQGHQF\ RI ]LUFRQLXP LRQV WR FURVVOLQN WKH SKRVSKRQDWH JURXSV SUHFOXGHV WKH QRUPDO GHSRVLWLRQ RI RUJDQRSKRVSKRQDWH PRQROD\HUV ZLWK WKH PHWDO LQ WKH VXESKDVH 7KHUHIRUH D SUHYLRXVO\ GHYHORSHG WKUHHVWHS GHSRVLWLRQ SURFHGXUH ZDV XVHG )LJXUH f DV GHVFULEHG LQ &KDSWHU %RWK V\PPHWULF 3G3=U3G3f DQG DOWHUQDWLQJ 2'3$=U3G3f ILOPV KDYH EHHQ SUHSDUHG LQ WKLV ZD\ )LJXUH f D E F G )LJXUH 6FKHPDWLF RI 3GSRUSK\ULQ ILOPV IRUPHG Df DOWHUQDWLQJ 2'3$=U3G3 Ef DOWHUQDWLQJ 2'3$=U3G32'3$ PL[HG ILOP Ff V\PPHWULF 3G3=U3G3 Gf V\PPHWULF 3G3 2'3$=U3G3 2'3 $ &RQWURO RYHU DJJUHJDWLRQ RI WKH SRUSK\ULQ FKURPRSKRUHV LV DFKLHYHG WKURXJK D FRPELQDWLRQ RI PROHFXODU GHVLJQ DQG WKH FDUHIXO FKRLFH RI WKH FRQGLWLRQV IRU WUDQVIHU

PAGE 75

RI WKH ILOPV $JJUHJDWLRQ LV GHFUHDVHG RU HOLPLQDWHG LQ WKH ILOPV RI WKH WHWUD VXEVWLWXWHG 3G3 ZKHQ WUDQVIHUUHG DW YHU\ KLJK PHDQ PROHFXODU DUHD 00$ DQG DW KLJK VXESKDVH S+ 0L[WXUHV RI WKLV DPSKLSKLOH ZLWK 2'3$ WUDQVIHUUHG DW KLJK WHPSHUDWXUHV r&f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f LV SUHVHQW DERYH QP DQG WZR 4 %DQGV DUH FHQWHUHG DURXQG QP! 6ROXWLRQ VWXGLHV RI WKH SRUSK\ULQV 3G3 DQG 3G3O ZHUH SHUIRUPHG LQ HWKDQRO DQG FKORURIRUP DQG WKH DEVRUEDQFH GHSHQGHQFH RQ FRQFHQWUDWLRQ ZDV LQYHVWLJDWHG 6ROXWLRQV UDQJLQJ IURP O2r 0 WR n 0 ZHUH VWXGLHG )LJXUH f ,Q &+&, WKH 6RUHW %DQG ZDV FRQVLVWHQWO\ DW WR QP IRU WKH SRUSK\ULQ 3G3 ,Q &+&, WKHUHIRUH 3G3 VKRZV QR VLJQ RI VROXWLRQ DJJUHJDWLRQ )RU SRUSK\ULQ 3G3O DW 0 WKH 6RUHW %DQG DEVRUEHG DW QP KRZHYHU DV WKH FRQFHQWUDWLRQ ZDV UDLVHG WKH %DQG VKLIWHG WR QP %HFDXVH 3G3O KDV RQO\ RQH ORQJ FKDLQ VXEVWLWXHQW WKH OLNHOLKRRG RI DJJUHJDWLRQ LV LQFUHDVHG WKHUHIRUH LQ &+& WKH 3G3O FKURPRSKRUHV DJJUHJDWH DW KLJK FRQFHQWUDWLRQV ,QWHUHVWLQJO\ WKH 6RUHW %DQGV IRU ERWK 3G3

PAGE 76

DQG 3G3O DEVRUE DW QP DW r 0 VR WKH ORQJ FKDLQV KDYH QR HIIHFW RQ WKH 6RUHW %DQG RI WKH QRQDJJUHJDWHG FKURPRSKRUH )LJXUH 6ROXWLRQ 89YLV RI 3GSRUSK\ULQV LQ &+& $f 3G3 %f 3G3O 7KH DEVRUEDQFH VFDOH UHIHUV WR WKH &7 0 FXUYH 7KH n 0 FXUYH KDV EHHQ HQODUJHG IRU %DQG FRPSDULVRQ 7KH VWXGLHV RI WKH VDPH PROHFXOHV DW LGHQWLFDO FRQFHQWUDWLRQV LQ (W2+ DQG ZDWHU VKRZHG YHU\ GLIIHUHQW EHKDYLRU )LJXUH f ,Q (W2+ DW n 0 ERWK 3G3 DQG 3G3O VKRZ 6RUHW %DQGV DW QP 7KLV SHDN LV VLJQLILFDQWO\ WR WKH UHG RI WKH 6RUHW %DQGV LQ &+&, KRZHYHU LW LV NQRZQ WKDW PRUH SRODU VROYHQWV WHQG WR VWDELOL]H

PAGE 77

WKH H[FLWHG VWDWHV LQ WWr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f YV DUHD 00$f LVRWKHUP RI 3G3 RQ ZDWHU DW S+ LV VKRZQ LQ )LJXUH 7KHUH LV D PHDVXUDEOH RQVHW RI VXUIDFH SUHVVXUH QHDU ƒ PROHFXOHn IROORZHG E\ D JUDGXDO LQFUHDVH LQ SUHVVXUH DV WKH ILOP LV FRPSUHVVHG ZLWK DQ DSSDUHQW SKDVH WUDQVLWLRQ JLYLQJ D VWHHSHU ULVH LQ SUHVVXUH QHDU

PAGE 78

ƒ PROHFXOH 7KH 00 $ RI WKH WHWUDSKHQ\O SRUSK\ULQ LV ƒ PROHFXOH LPSO\LQJ WKDW DW WKH RQVHW WKH WHWUDVXEVWLWXWHG SRUSK\ULQ PROHFXOHV DUH QRW DJJUHJDWHG RU VWDFNHG +RZHYHU WKLV DUUDQJHPHQW LV QRW VWDEOH WR SUHVVXUH DQG DV WKH ILOP LV FRPSUHVVHG WKH PROHFXOHV DUH IRUFHG WR UHDUUDQJH )LJXUH ,VRWKHUPV RI 3G3 SXUH DQG PL[HG ZLWK 2'3$ 3G32'3$f RQ D ZDWHU VXESKDVH 7KH FKDQJH LQ WKH DJJUHJDWLRQ RI 3G3 GXULQJ FRPSUHVVLRQ FDQ EH REVHUYHG ZLWK UHIOHFWDQFH 89YLV VSHFWURVFRS\ RI WKH /DQJPXLU PRQROD\HU )LJXUH f $V WKH ILOP LV FRPSUHVVHG IURP D 00$ RI ƒ PROHFXOH WKURXJK $ PROHFXOH WKH $PD[ UHPDLQV EHWZHHQ DQG QP VLPLODU WR WKH PD[ REVHUYHG IRU WKH QRQ DJJUHJDWHG SRUSK\ULQ LQ (W2+ $W DUHDV EHWZHHQ DQG $ PROHFXOH WKH 6RUHW %DQG VKLIWV WR QP DQG EHORZ ƒ PROHFXOH WKH 6RUHW %DQG VKLIWV IXUWKHU WR QHDU QP 7KH VKLIW LQ WKH 6RUHW %DQG VXJJHVWV D FKDQJH LQ WKH

PAGE 79

LQWHUDFWLRQ RI WKH FKURPRSKRUHV DW GLIIHUHQW SUHVVXUHV $W 00$ ODUJHU WKDQ DQG FRPSDUDEOH WR WKH VL]H RI WKH FKURPRSKRUH LWVHOI WKH SRUSK\ULQ ULQJV FDQQRW EH DJJUHJDWLQJ WR DQ\ VLJQLILFDQW H[WHQW RU WKH RQVHW RI VXUIDFH SUHVVXUH ZRXOG RFFXU DW ORZHU DUHDV 7KH UHG VKLIW RI WKH 6RUHW %DQG DV WKH DUHD LV GHFUHDVHG LQGLFDWHV HQKDQFHG FKURPRSKRUH DJJUHJDWLRQ DW ORZHU 00$ )LJXUH 5HIOHFWDQFH 89YLV RI 3G3 RQ ZDWHU VXESKDVH ,Q FRQWUDVW WR 3G3 WKH ,7$ LVRWKHUP RI 3G3O )LJXUH f LQGLFDWHV WKDW WKHVH PROHFXOHV DJJUHJDWH HYHQ LQ WKH DEVHQFH RI DSSOLHG SUHVVXUH 1R VLJQLILFDQW LQFUHDVH LQ VXUIDFH SUHVVXUH LV VHHQ XQWLO DUHDV EHORZ ƒ PROHFXOH 7KH SUHVVXUH ULVHV WR RQO\ P1 P DW ƒ PROHFXOH EHORZ ZKLFK WKH SUHVVXUH LQFUHDVHV XQWLO WKH ILOP FROODSVHV EHORZ ƒ PROHFXOH 7KH LVRWKHUP FDQQRW UHIOHFW D WUXH PROHFXODU PRQROD\HU EXW UDWKHU UHVXOWV IURP WKH FRPSUHVVLRQ RI DJJUHJDWHV DW WKH ZDWHU VXUIDFH

PAGE 80

(YLGHQFH RI DJJUHJDWLRQ DW DOO 00$ LV VHHQ LQ WKH UHIOHFWDQFH 89YLV VSHFWUD )LJXUH VKRZV WKH 6RUHW %DQG DV D IXQFWLRQ RI 00$ IURP JUHDWHU WKDQ ƒ PROHFXOHn WR ILOP FROODSVH DW ƒ PROHFXOHn 7KH 6RUHW %DQG GRHV QRW VKLIW GXULQJ FRPSUHVVLRQ DQG WKH ;PD[ RI QP LQGLFDWHV WKDW WKH SRUSK\ULQV DUH DJJUHJDWHG DW HDFK VWDJH RI WKH LVRWKHUP )LJXUH ,VRWKHUPV RI 3G3O SXUH DQG PL[HG ZLWK 2'3$ 3G3O 2'3$f RQ D ZDWHU VXESKDVH $ FRPPRQ SURFHGXUH IRU HQKDQFLQJ WKH VWDELOLW\ DQG SURFHVVLELOLW\ RI XQVWDEOH /DQJPXLU PRQROD\HUV DQG WR UHGXFH DJJUHJDWLRQ LV WR PL[ WKH DPSKLSKLOH RI LQWHUHVW ZLWK D JRRG ILOPIRUPLQJ DPSKLSKLOHfn ,Q WKLV SXUVXLW ERWK RI WKH SRUSK\ULQV ZHUH PL[HG ZLWK 2'3$ ZKLFK LV D ZHOOVWXGLHG DPSKLSKLOH WKDW IRUPV D OLTXLG FRQGHQVHG SKDVH RQ WKH ZDWHU VXUIDFH DQG HDVLO\ ELQGV WR DQ H[SRVHG =USKRVSKRQDWH VXUIDFH $V WKH SHUFHQWDJH RI 2'3$ LV LQFUHDVHG WKH LVRWKHUPV LQFUHDVLQJO\ WDNH RQ

PAGE 81

FKDUDFWHULVWLFV RI WKH OLTXLGFRQGHQVHG SKDVH RI 2'3$ DOWKRXJK IHDWXUHV SUHVHQW LQ WKH LVRWKHUPV RI WKH SXUH SRUSK\ULQV DUH DOVR SUHVHQW LQ WKH LVRWKHUPV RI WKH PL[HG ILOPV )LJXUH DQG f :DYHOHQJWK QPf )LJXUH 5HIOHFWDQFH 89YLV RI 3G3O RQ ZDWHU VXESKDVH ,Q DGGLWLRQ WKH FROODSVH SUHVVXUH LQFUHDVHV ZLWK WKH FRQFHQWUDWLRQ RI 2'3$ LQGLFDWLQJ WKDW WKH ILOPV EHFRPH PRUH VWDEOH DV 2'3$ LV DGGHG +RZHYHU GLOXWLQJ WKH SRUSK\ULQ ILOP ZLWK 2'3$ GRHV QRW DSSHDU WR JUHDWO\ DIIHFW WKH DJJUHJDWLRQ 5HIOHFWDQFH 89 YLV RI D /DQJPXLU PRQROD\HU RI D PL[WXUH RI 3G3 ZLWK 2'3$ LV VKRZQ LQ )LJXUH 7KH PD[ VKLIWV IURP QP DW KLJK 00$ WR QP DV WKH ILOP LV FRPSUHVVHG MXVW DV LW GRHV LQ WKH ILOPV RI SXUH 3G3 )LJXUH f +RZHYHU WKH SRUSK\ULQV GR QRW DSSHDU WR EH DJJUHJDWHG LQ WKH PL[HG ILOP DW KLJK 00$

PAGE 82

)LJXUH 5HIOHFWDQFH 89YLV RI b 3G3 b 2'3$ RQ D ZDWHU VXESKDVH 7KH PROHFXODU DUHDV LQ )LJXUHV DQG DUH ZHLJKWHG DYHUDJHV RI WKH SRUSK\ULQ DQG 2'3$ PROHFXOHV 7KH 00$ RI WKH SRUSK\ULQ PROHFXOHV LQ WKH PL[HG ILOPV FDQ EH FDOFXODWHG XVLQJ (TXDWLRQ A0L[ f§ 695 16TWD f 1f f ZKHUH 6Pc[ LV WKH 00$ RI WKH PL[WXUH GHWHUPLQHG IURP WKH LVRWKHUP 6SRU LV WKH 00$ RI WKH SRUSK\ULQ ZLWKLQ WKH PL[HG ILOPV 6RGSD LV WKH 00$ RI WKH 2'3$ DPSKLSKLOH LQ SXUH 2'3$ ILOPV DQG 1 LV WKH PRODU UDWLR RI 2'3$ WR SRUSK\ULQ 6SRU ZDV FDOFXODWHG LQ WKH 2'3$ PL[WXUHV RI HDFK SRUSK\ULQ DW SUHVVXUHV RI P1 QU DQG P1 QU DQG WKH UHVXOWV DUH SORWWHG LQ )LJXUH

PAGE 83

)LJXUH 0HDQ PROHFXODU DUHD YV UDWLR RI 2'3$3RUSK\ULQ $f 3G3 %f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f ,W KDV EHHQ VKRZQ WKDW D ]LUFRQDWHG 2'3$ WHPSODWH OD\HU IUHTXHQWO\ SURYLGHV WKH EHVW VXEVWUDWH IRU WUDQVIHUULQJ D FDSSLQJ OD\HU

PAGE 84

7KH H[WUHPHO\ ZHOO RUJDQL]HG DQG R[RSKLOLF VXUIDFH DOORZV GHSRVLWLRQ RI DOPRVW DQ\ SKRVSKRQLF DFLG PRQROD\HU LQFOXGLQJ WKRVH WKDW DUH QRW VWDEOH PRQROD\HUV DQG ZRXOG QRUPDOO\ QRW WUDQVIHU 0RQROD\HUV RI 3G3 DQG 3G3O ZHUH WUDQVIHUUHG DW D UDQJH RI WHPSHUDWXUHV SUHVVXUHV DQG VXESKDVH S+V 7DEOHV DQG f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ƒ PROHFXOHf P1 QUf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f DQG ƒ PROHFXOHf )LJXUH f 7KH 6RUHW %DQG VKLIWV WR QP IRU WKH ILOP WUDQVIHUUHG DW ƒ PROHFXOHf DQG WR QP IRU WKH ILOP WUDQVIHUUHG DW ƒ PROHFXOHf LQGLFDWLQJ OHVV DJJUHJDWLRQ LQ ILOPV WUDQVIHUUHG DW KLJK 00$ $W WKHVH ODUJHU 00$ WKH SRUSK\ULQ FKURPRSKRUHV VKRXOG EH O\LQJ IODW DW WKH DLUZDWHU LQWHUIDFH ZLWK OLWWOH DJJUHJDWLRQ DQG WKH\ DSSHDU WR UHPDLQ QRQLQWHUDFWLQJ ZKHQ WUDQVIHUUHG

PAGE 85

7DEOH 89YLV GDWD IURP V\PPHWULF DQG DOWHUQDWLQJ ILOPV RI 3G3 $PD[ LV JLYHQ IRU PRQROD\HUV DQG LQWHUOD\HU WKLFNQHVV LV JLYHQ IRU PXOWLOD\HUV RI ILOPV WUDQVIHUUHG XQGHU D YDULHW\ RI WUDQVIHU FRQGLWLRQV )LOP 7UDQVIHU $UHD ƒ PROnfr ULRI 7UDQVIHU P1Pf S+rrr 7HPS r&f APD[ QPf WKLFNQHVV $f 23$=U3G3 23$=U 3G3 23$=U 3G3 f§ 23$=U 3G3 f§ 23$=U 3G3 f§ 23$=U 3G3 f§ 23$=Ub 3G3 f§ 23$=Ub 3G3 23$=Ub 3G3 f§ 23$=Ub 3G3 f§ 23$=U 3G3 f§ 23$=U 3G3 f§ 23$=U 3G3 f§ f§ 23$=U 3G3 f§ 23$=U 3G3 f§ 23$=Ub 3G3 f§ 23$=Ub 3G3 f§ 23$=Ub 3G3 23$=Ub 3G3 f§ 3G3=U 3G3 f§ 3G3=U 3G3 f§ b 3G3=U b 3G3 r $UHD RI WKH FKURPRSKRUH DQG GLOXHQW DV GHWHUPLQHG IURP )LJXUH LVRWKHUPVf rr &RUUHVSRQGLQJ SUHVVXUH IURP )LJXUH LVRWKHUPf rrr S+ RI QDQRSXUH ZDWHU IURP ILOWUDWLRQ V\VWHP LV DERXW

PAGE 86

)LJXUH 7UDQVPLVVLRQ 89YLV RI 3G3 ILOPV WUDQVIHUUHG DW KLJK DQG ORZ 00$ $EVRUEDQFH VFDOH FRUUHVSRQGV WR WKH ILOP WUDQVIHUUHG DW ƒ PROHFXOHn 7KH DEVRUEDQFH IRU WKH ILOP WUDQVIHUUHG DW ƒ PROHFXOHn KDV EHHQ GLYLGHG E\ $V WKH S+ ZDV UDLVHG WKH DPSKLSKLOHV EHFDPH VOLJKWO\ PRUH ZDWHUVROXEOH DQG WKH PRQROD\HU ZDV LQFUHDVLQJO\ VXVFHSWLEOH WR FUHHS +RZHYHU ILOPV RI 3G3 FRPSUHVVHG WR ƒ PROHFXOH ZHUH GHSRVLWHG RQWR ]LUFRQDWHG 2'3$ WHPSODWHV IURP VXESKDVHV RI S+ DQG $V WKH S+ LQFUHDVHG $PD[ RI WKH 6RUHW %DQG RI WKH WUDQVIHUUHG ILOP GHFUHDVHG WR QP IRU WKH ILOP GHSRVLWHG DW S+ 7KLV ZDV WKH ORZHVW YDOXH RI ;PD[ DQG WKHUHIRUH WKH OHDVW DJJUHJDWHG /% WUDQVIHUUHG ILOP RI 3G3 7KH ;PD[ RI WKLV 6RUHW %DQG FRUUHVSRQGV WR WKDW RI FKURPRSKRUH 3G3 LQ (W2+ DW 0 ZKLFK LV EHOLHYHG WR EH QRQDJJUHJDWHG &RQVLVWHQWO\ s ZKHQ PHDVXUHG DW r LQFLGHQFH LQGLFDWLQJ QR SUHIHUUHG LQSODQH RULHQWDWLRQ RI WKH FKURPRSKRUH LQ WKH 3G3 DQG 3G3O ILOPV +RZHYHU LQ DOO ILOPV r ZKHQ PHDVXUHG DW LQFLGHQFH )RU ILOPV WUDQVIHUUHG DW KLJK VXUIDFH DUHD LW LV H[SHFWHG WKDW WKH SRUSK\ULQV VKRXOG OLH IODW ZLWK DOO IRXU SKRVSKRQDWHV WHWKHUHG WR WKH VXUIDFH ,QGHHG WKLV LV REVHUYHG IRU ILOPV WUDQVIHUUHG DW

PAGE 87

ƒ PROHFXOHn DQG ƒ PROHFXOH ZKHUH WKH WLOW DQJOH ZLWK UHVSHFW WR WKH VXUIDFH QRUPDO LV REVHUYHG WR EH r ,QWHUHVWLQJO\ WKH SRUSK\ULQV DOVR DSSHDU WR OLH SDUDOOHO WR WKH VXUIDFH LQ WKH ILOPV WUDQVIHUUHG DW ƒ PROHFXOHn ZKHUH LV DOVR PHDVXUHG DV DSSUR[LPDWHO\ r 7KLV UHVXOW LPSOLHV WKDW LQ ILOPV WUDQVIHUUHG DW DUHDV VPDOOHU WKDQ WKH 00$ RI WKH IODW SRUSK\ULQ PDFURF\FOH WKH PROHFXOHV RYHUODS VWDFNLQJ LQ ELOD\HUV RU PXOWLOD\HUV EXW ZLWK YHU\ OLWWOH FKDQJH LQ WKH WLOW DQJOH 7KHUH LV D ODUJHU XQFHUWDLQW\ SRVVLEO\ s r LQ WKH PHDVXUHPHQW DV WKH WLOW DQJOHV QHDU r KRZHYHU WKHVH UHVXOWV FRQILUP WKDW WKH FKURPRSKRUHV DUH O\LQJ DSSUR[LPDWHO\ IODW LQ DOO RI WKH ILOPV LQ WKLV VWXG\ 0XOWLOD\HUV RI WKH DOWHUQDWLQJ 2'3$=U3G3 ILOPV FDQ EH GHSRVLWHG DQG ;UD\ GLIIUDFWLRQ FRQILUPV WKH OD\HUHG QDWXUH RI WKH ILOPV 7ZR RU WKUHH RUGHUV RI WKH f %UDJJ SHDNV FDQ EH REVHUYHG LQ HDFK FDVH )LOPV WUDQVIHUUHG DW ƒ PROHFXOHn KDYH D ELOD\HU WKLFNQHVV RI ƒ ZKLFK LV VPDOOHU WKDQ WKH ƒ WKLFNQHVV VHHQ LQ SXUH 2'3$=U2'3$ ELOD\HUV VXJJHVWLQJ WKDW WKH FDUERQ WHWKHUV RI 3G3 DUH QRW IXOO\ H[WHQGHG LQ WKH DOWHUQDWLQJ ILOPV )RU WKH ILOP WUDQVIHUUHG DW ƒ PROHFXOH WKH ELOD\HU WKLFNQHVV LQFUHDVHV WR ƒ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f %UDJJ SHDNV FRXOG QRW EH VHHQ LQ GLIIUDFWLRQ IURP

PAGE 88

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b 3G3 ZLWK 2'3$ WUDQVIHUUHG DW P1 QU RQ D VXESKDVH KHDWHG WR r & VKRZV D 6RUHW %DQG $PD[ RI QP VKLIWHG IURP QP IRU WKH VDPH ILOP GHSRVLWHG DW URRP WHPSHUDWXUH $V WKH VXESKDVH LV KHDWHG WKH DJJUHJDWHV DSSHDU WR EUHDNXS LQ WKH PL[HG ILOP $ VLPLODU HIIHFW LV QRW VHHQ RQ WKH SXUH ILOPV RI 3G3 ,W DSSHDUV WKDW WKH 2'3$ SOD\V D UROH LQ EUHDNLQJ XS WKH DJJUHJDWHG GRPDLQV DW KLJKHU WHPSHUDWXUHV )LOPV RI 3G3 ZHUH DOVR SUHSDUHG E\ WKH 6$ WHFKQLTXH $IWHU WKH ]LUFRQDWHG 2'3$ WHPSODWH KDG EHHQ H[SRVHG WR D 3G3 VROXWLRQ LQ (W2++ IRU KU WKH SRUSK\ULQV ZHUH VXFFHVVIXOO\ LQFRUSRUDWHG LQWR WKHVH ILOPV 7KH 6RUHW %DQG DSSHDUHG DW QP ZKLFK WKHQ VKLIWHG WR QP DIWHU PLQ ULQVLQJ LQ KRW &+& 7KH $PD[ LQ WKH 6$ ILOP ZDV WKH FORVHVW RI DQ\ RI WKH 3G3 ILOPV WR WKDW VHHQ LQ WKH GLOXWH VROXWLRQ 7KHUHIRUH LW DSSHDUV WKDW QRQDJJUHJDWHG DVVHPEOLHV RI 3G3 DUH HDVLO\ REWDLQHG E\ VHOIDVVHPEO\ )LJXUH f +RZHYHU WKH RYHUDOO DEVRUEDQFH LQWHQVLW\ RI WKHVH QRQDJJUHJDWHG ILOPV LV ORZHU WKDQ REVHUYHG LQ WKH ILOPV WUDQVIHUUHG E\ WKH /% WHFKQLTXH DW KLJK 00$

PAGE 89

:DYHOHQJWK QPf )LJXUH 89YLV RI 6$ 3G3 ILOPV ULQVHG LQ KRW &+& )LOPV RI FRPSRXQG 3G3O 7KH ),$ LVRWKHUPV DQG WKH UHIOHFWDQFH 89YLV H[SHULPHQWV GHVFULEHG DERYH LQGLFDWH WKDW WKH PROHFXOHV RI 3G3O DJJUHJDWH XSRQ VSUHDGLQJ DQG WKLV DJJUHJDWLRQ LV SUHVHUYHG LQ WKH WUDQVIHUUHG ILOPV ,Q FRQWUDVW WR 3G3 WKH PRQRSKRVSKRQDWH 3G3O LV RQO\ VOLJKWO\ LQIOXHQFHG E\ DWWHPSWV WR EUHDN XS WKH DJJUHJDWHV E\ FKDQJLQJ WKH GHSRVLWLRQ FRQGLWLRQV 7KH 89YLV VSHFWUXP RI D FDSSLQJ OD\HU RI 3G3O WUDQVIHUUHG DW ƒ PROHFXOHr P1 QUf LV VKRZQ LQ )LJXUH ZKHUH WKH 6RUHW %DQG DSSHDUV DW QP FRQVLVWHQW ZLWK WKH YDOXH REVHUYHG LQ WKH UHIOHFWDQFH VSHFWUXP WDNHQ IURP WKH ZDWHU LQWHUIDFH 7KH VKDSH RI WKH 6RUHW %DQG GRHV QRW FKDQJH IRU ILOPV GHSRVLWHG DW KLJKHU 00$ KLJKHU WHPSHUDWXUHV RU LQ PL[WXUHV ZLWK 2'3$ 7KH SHDN SRVLWLRQ VKLIWV RQO\ VOLJKWO\ 7DEOH f 7KH RULHQWDWLRQ RI WKH FKURPRSKRUHV ZHUH DOVR XQDIIHFWHG E\ WKH GHSRVLWLRQ FRQGLWLRQV 3RODUL]HG VSHFWUD FRQVLVWHQWO\ JLYH WLOW DQJOHV RI r FRUUHVSRQGLQJ WR WKH SRUSK\ULQV O\LQJ IODW

PAGE 90

)LJXUH 7UDQVPLVVLRQ 89YLV RI ILOPV RI 3G3O WUDQVIHUUHG DW KLJK DQG ORZ 00$ ;UD\ GLIIUDFWLRQ IURP DOWHUQDWLQJ ILOPV RI 3G3O WUDQVIHUUHG DW ƒ PROHFXOHn RQWR D ]LUFRQDWHG 2'3$ WHPSODWH JLYHV D OD\HU WKLFNQHVV RI ƒ 7DEOH f 7KLV WKLFNQHVV LV ODUJHU WKDQ WKDW RI WKH DOWHUQDWLQJ ILOPV RI 2'3$=U3G3 RU 2'3$=U2'3$ ELOD\HUV 6LQFH RSWLFDO VSHFWURVFRS\ LQGLFDWHV WKH PROHFXOHV OLH IODW WKH HQKDQFHG WKLFNQHVV RI WKH OD\HU VXJJHVWV WKH\ WUDQVIHU DV VWDFNHG ELOD\HUV RU PXOWLOD\HUV )XUWKHU HYLGHQFH IRU WKLV DUUDQJHPHQW FRPHV IURP WKH ILOP VWDELOLW\ VWXGLHV GHVFULEHG EHORZ ZKLFK LQGLFDWH WKDW SDUW RI WKH WUDQVIHUUHG ILOP RI SRUSK\ULQ 3G3O LV SK\VLVRUEHG WR WKH VXUIDFH

PAGE 91

7DEOH 89YLV GDWD IURP V\PPHWULF DQG DOWHUQDWLQJ ILOPV RI 3G3O ;P][ LV JLYHQ IRU PRQROD\HUV DQG LQWHUOD\HU WKLFNQHVV LV JLYHQ IRU PXOWLOD\HUV RI ILOPV WUDQVIHUUHG XQGHU D YDULHW\ RI WUDQVIHU FRQGLWLRQV )LOP $UHD RI 7UDQVIHU ƒ9PROHFXOHfr ULRI 7UDQVIHU P1Pf 7HPS r&f QPf WKLFNQHVV ƒf 23$=U3G3O 23$=U3G3 23$=U 3G3O f§ 23$=U 3G3O f§ 23$=U 3G3O f§ 23$=Ub 3G3O 23$=Ub f§ 3G3O 23$=Ub f§ 3G3O 23$=U3G3O f§ 23$=U 3G3O f§ 23$=U 3G3O f§ f§ 23$=U3G3O f§ 23$=Ub 3G3O 23$=Ub f§ 3G3O 23$=Ub 3G3O 3G3O=U 3G3O f§ b 3G3O=U b 3G3O r $UHD RI WKH FKURPRSKRUH DQG GLOXHQW DV GHWHUPLQHG IURP )LJXUH LVRWKHUPVf rr &RUUHVSRQGLQJ SUHVVXUH IURP )LJXUH LVRWKHUPf rrr S+ RI QDQRSXUH ZDWHU IURP ILOWUDWLRQ V\VWHP LV DERXW

PAGE 92

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f 7KLV UHVXOW VXJJHVWV WKDW WKH VWDFNHG OD\HUV RI FKURPRSKRUHV LQ WKH SRUSK\ULQ 3G3O ILOPV ZHUH SDUWLDOO\ SK\VLVRUEHG RQ WKH VXUIDFH )LJXUH $EVRUEDQFH RI 6RUHW YV WLPH ULQVHG LQ KRW &+& Df 3G3 Ef 3G3O

PAGE 93

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

PAGE 94

&KHPLFDO PRGLILFDWLRQ ZLWK IRXU DON\OSKRVSKRQLF DFLG VLGHJURXSV DOORZV WKH SRUSK\ULQ WR VSUHDG FRPSOHWHO\ 3RUSK\ULQ 3G3 VSUHDGV WR D PRQROD\HU WKLFN ILOP DW KLJK 00$ DQG DV WKH ILOP LV FRPSUHVVHG DQ LQFUHDVH LQ VXUIDFH SUHVVXUH LV UHJLVWHUHG QHDU ƒ PROHFXOHr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

PAGE 95

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

PAGE 96

2'3$ WHPSODWH OD\HU DOORZV DOPRVW DQ\ SKRVSKRQLF DFLG GHULYDWL]HG DPSKLSKLOH WR WUDQVIHU LQ D FDSSLQJ OD\HUff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

PAGE 97

&+$37(5 0$1*$1(6( 3253+<5,1 &217$,1,1* =,5&21,80 3+263+21$7( 7+,1 ),/06 %DFNJURXQG 0RQROD\HU DQG ILOP ZRUN XVLQJ WKH PROHFXOH PDQJDQHVH WHWUDNLVWHWUDIOXRURSKHQ\ORFWDGHF\OR[\SKRVSKRQLF DFLGfSRUSK\ULQ RU 0Q3 ZLOO EH GLVFXVVHG LQ &KDSWHU )LJXUH $f )RU FRPSDULVRQ ZRUN GRQH XVLQJ D VLPLODU PROHFXOH ZLWKRXW WKH IRXU DON\OSKRVSKRQLF DFLG FKDLQV PDQJDQHVH WHWUDNLVSHQWDIOXRURSKHQ\OfSRUSK\ULQ RU 0Q32 ZLOO DOVR EH GLVFXVVHG )LJXUH ,%f 7KH PDQJDQHVH SRUSK\ULQV DUH VWUXFWXUDOO\ DQG FKHPLFDOO\ PRUH FRPSOH[ WKDQ WKH SDOODGLXP SRUSK\ULQV 7KH 0Q,,,f FHQWUDO PHWDO LV D RU FRRUGLQDWH G PHWDOVR 'HSHQGLQJ RQ WKH OLJDQG FKDUDFWHU 0Q,,,f LV HLWKHU 6 KLJK VSLQf RU 6 ORZ VSLQf $OVR GHSHQGLQJ RQ WKH D[LDO OLJDQG RU OLJDQGV WKH 0Q,,,f PD\ RU PD\ QRW EH FRSODQDU ZLWK WKH SRUSK\ULQ OLJDQG 0Q,,,f DOVR KDV DQ HDVLO\ DFFHVVLEOH ORZHU R[LGDWLRQ VWDWH ZKLFK OHDGV WR VLJQLILFDQW PHWDOSRUSK\ULQ HOHFWURQLF LQWHUDFWLRQV WKH 0Q,,,fSRUSK\ULQV KDYH D WHQGHQF\ WR IRUP IDFHWRIDFH GLPHUV EULGJHG WKURXJK DQ D[LDO OLJDQG DQG WKH 0Q,,,fSRUSK\ULQV DUH YXOQHUDEOH WR GHPHWDOODWLRQ XQGHU FHUWDLQ FRQGLWLRQV 7KHUHIRUH ILOP FKDUDFWHUL]DWLRQ XVLQJ WKHVH PROHFXOHV ZDV PXFK PRUH FRPSOLFDWHG WKDQ ZLWK WKH 3GSRUSK\ULQV 7R LQYHVWLJDWH WKH FDWDO\WLF SURSHUWLHV RI PDQJDQHVHSRUSK\ULQ ILOPV ILOP SUHSDUDWLRQ SURFHGXUHV LQYROYLQJ WKH WHWKHULQJ RI 0QSRUSK\ULQV WR D PHWDO

PAGE 98

SKRVSKRQDWH QHWZRUN ZHUH GHYHORSHG 7KLV PHWKRG LQYROYHV WKH LQLWLDO IRUPDWLRQ RI D ]LUFRQDWHG RFWDGHF\OSKRVSKRQLF DFLG 2'3$f WHPSODWH RQWR ZKLFK D ILOP RI SXUH 0Q3 FDQ EH 6$ RU WUDQVIHUUHG YLD WKH /% WHFKQLTXH )LJXUH f ,QFOXGLQJ 0Q3 LQ D ]LUFRQLXP SKRVSKRQDWH QHWZRUN SURYLGHG ILOPV WKDW ZHUH VWDEOH WRZDUG KDUVK RUJDQLF FRQGLWLRQV $OVR WKH VWURQJ R[RSKLOLFLW\ RI WKH ]LUFRQLXP IRU WKH SKRVSKRQDWH R[\JHQV HQDEOHG WKH ILOP SUHSDUDWLRQ SURFHGXUH WR EH HDVLO\ DOWHUHG DQG ILQH WXQHG DQG FRPSOHWH ILOP FKDUDFWHUL]DWLRQ WR EH FDUULHG RXW )LJXUH 6WUXFWXUHV RI $f 0Q3 DQG %f 0Q32 7KH 0Q3 PROHFXOH LV VLPLODU WR WKH 3G3 PROHFXOH GHVFULEHG LQ &KDSWHU LQ ZKLFK WKH PDQJDQHVH WHWUDSKHQ\OSRUSK\ULQ 0Q733f FKURPRSKRUH DQG WKH VWURQJO\ K\GURSKLOLF SKRVSKRQDWH JURXSV DUH VHSDUDWHG E\ FDUERQ FKDLQV )LJXUH $f 7KLV JHRPHWU\ DOORZHG IRU WKH SRUSK\ULQ WR EH VLWWLQJ DW WKH H[WHULRU RI WKH ILOP DQG DYDLODEOH IRU FDWDO\VLV ZKLOH WKH SKRVSKRQDWHV ZHUH EXULHG LQ WKH K\GURSKLOLF UHJLRQ DQG DYDLODEOH IRU ELQGLQJ WR WKH VWDELOL]LQJ LQRUJDQLF QHWZRUN 7KH LQFRUSRUDWLRQ RI WKLV QHWZRUN VLJQLILFDQWO\ LPSURYHV WKH UHVLVWDQFH RI WKH ILOP WR W\SLFDOO\ GHVWUXFWLYH

PAGE 99

IRUFHV VXFK DV VROYHQW KHDW RU WLPH ,Q DGGLWLRQ KDYLQJ IRXU DPSKLSKLOLF FKDLQV RQ WKH SRUSK\ULQ SHUPLWV WKH IRUPDWLRQ RI /DQJPXLU PRQROD\HUV RI WKHVH PDWHULDOV ZLWKRXW GLOXWLQJ WKH DPSKLSKLOHV ZLWK D JRRG ILOP IRUPLQJ DPSKLSKLOH VXFK DV VWHDULF DFLG 7KH 0Q3 ILOPV ZHUH ILUVW LQYHVWLJDWHG RQ WKH ZDWHU VXUIDFH LQ D /DQJPXLU PRQROD\HU $Q LVRWKHUP RI WKLV PDWHULDO VKRZHG VLJQLILFDQW ILOP FRPSUHVVLELOLW\ )LJXUH f 5HIOHFWDQFH 89YLV VKRZHG WKDW WKH SRUSK\ULQV IRUPHG IDFHWRIDFH GLPHUV DERYH FD P1 Pn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fSRUSK\ULQV KDYH DEVRUSWLRQ VSHFWUD VLPLODU WR IUHHEDVH SRUSK\ULQV GXH WR D ODFN RI PHWDOSRUSK\ULQ LQWHUDFWLRQ KRZHYHU WKH DEVRUSWLRQ VSHFWUXP RI WKH 0Q,,,fSRUSK\ULQ LV TXLWH GLIIHUHQW $FFRUGLQJ WR *RXWHUPDQ 0Q,,,f733 LV D FODVVLF GW\SH K\SHUSRUSK\ULQ ZLWK H[WUD DEVRUSWLRQ EDQGV DW KLJKHU

PAGE 100

HQHUJLHV UHODWLYH WR ;PD[ 7KH 0Q3 DQG 0Q32 ZLWK FKORULGH D[LDO OLJDQGV DUH VSHFWUDOO\ FRQVLVWHQW ZLWK G SRUSK\ULQV LQ KLJKVSLQ FRQILJXUDWLRQV 7KH VWURQJ DEVRUSWLRQ QHDU QP LV RIWHQ FDOOHG %DQG 9 GXH WR WKH IDFW WKDW WKLV WUDQVLWLRQ LV QRW SXUH QQr LQ QDWXUH EXW LQFOXGHV PHWDOSRUSK\ULQ RUELWDO PL[LQJ +RZHYHU WUDGLWLRQDOO\ LW LV VWLOO RIWHQ FDOOHG WKH 6RUHW %DQG 2QH VWURQJ EDQG FRPPRQO\ VHHQ WR WKH EOXH RI WKH 6RUHW %DQG LV FDOOHG %DQG 9, $ SURPLQHQW SHDN RIWHQ REVHUYHG VSHFLILFDOO\ LQ WKH 0Q3 89YLV VSHFWUXP FD QP LV UHIHUUHG WR DV %DQG 9D /LJDQG HIIHFWV DQG RULHQWDWLRQ RU DJJUHJDWLRQ HIIHFWV DUH UHIOHFWHG SULPDULO\ LQ WKH VKDSH RU VKLIW RI WKH 6RUHW %DQG DQG LQ WKH H[WLQFWLRQ FRHIILFLHQW Vf 7KHUHIRUH WKH EHKDYLRU RI WKLV EDQG ZDV FDUHIXOO\ PRQLWRUHG $OVR GLIIHUHQW VROYHQWV XVHG IRU SRUSK\ULQ LQYHVWLJDWLRQV FDXVHG FKDQJHV LQ WKH DEVRUSWLRQ VSHFWUD ,I D FRRUGLQDWLQJ VROYHQW ZDV XVHG WKH D[LDO OLJDQG ZDV GLVSODFHG E\ D VROYHQW PROHFXOH FDXVLQJ D VKLIW LQ WKH 6RUHW %DQG DQG LQ WKH 99, LQWHQVLW\ UDWLR 89YLV RI 0Q32 LQ VROXWLRQ $ FRQFHQWUDWLRQ VWXG\ RI 0Q32 LQ &+& VKRZHG WKDW WKH ;PD[ ZDV FRQVLVWHQWO\ DW QP EHWZHHQ DQG n 0 V [ 0n Pf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

PAGE 101

)LJXUH 89YLV RI 0Q32 LQ &+& 89YLV RI 0Q3 LQ VROXWLRQ 6LPLODU VROYHQW VKLIWV ZHUH REVHUYHG LQ WKH FDVH RI 0Q3 ,Q &+& RU &+& DW f 0 RU ORZHU FRQFHQWUDWLRQV WKH APD[ DSSHDUHG DW QP ZKHUHDV LQ (W2+ RU ZDWHU WKH V\PPHWULF 6RUHW %DQG RFFXUUHG DW QP )LJXUH f 7KH SHDN DW QP FRUUHVSRQGV WR WKH 0Q32 6RUHW %DQG LQ (W2)O LQGLFDWLQJ D VLPLODU D[LDO HQYLURQPHQW OLNHO\ D ELVHWKDQRO FRPSOH[ KRZHYHU D YHU\ FOHDU EDQG 9D ZDV SUHVHQW DW QP LQ WKH 0Q3 VROXWLRQV $GGLWLRQDOO\ WKH UDWLRV RI %DQG 9 WR 9, ZHUH GLIIHUHQW IRU HDFK GLIIHUHQW VROYHQW LPSO\LQJ WKDW FRRUGLQDWLQJ VROYHQWV HIIHFW WKH SRUSK\ULQ D[LDO HQYLURQPHQW 7KH REVHUYHG 0Q3 VSHFWUDO EHKDYLRU LQ &+& ZDV YHU\ GLIIHUHQW IURP WKH VSHFWUDO EHKDYLRU LQ (W2+ RU + $W n 0 WKH ;PD[ RFFXUV DW QP ZLWK D GLVWLQFW VKRXOGHU SUHVHQW RQ WKH UHG VLGH RI WKH 6RUHW %DQG $V WKH FRQFHQWUDWLRQ RI SRUSK\ULQ LQ &+& LQFUHDVHG IURP n 0 WR n 0 WKH UHG VKRXOGHU EHFDPH D GLVWLQFW VHFRQG SHDN DW QP )LJXUH f 7KH WZR SHDNV DUH KHUHDIWHU UHIHUUHG WR DV 9L DQG 9LL IRU

PAGE 102

WKH ILUVW DQG VHFRQG 6RUHW %DQGV 7KH SHDN DW QP ZDV LGHQWLILHG DV WKH IRUPDWLRQ RI D ILYHFRRUGLQDWH 0Q733 &O VWUXFWXUH LQ WKH FDVH RI 0Q32 LQ &+& DQG WKHUHIRUH LW FOHDUO\ UHSUHVHQWHG WKH DQDORJRXV VWUXFWXUH LQ 0Q3 )LJXUH f )LJXUH 6ROYHQW EHKDYLRU RI 0Q3 LQ ZDWHU (W2+ DQG &+& :DYHOHQJWK QPf )LJXUH 89YLV FRQFHQWUDWLRQ VWXG\ RI 0Q3 LQ &+& Df n 0 Ef n 0

PAGE 103

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f 7KLV FRPSRXQGfV VSHFWUDO EHKDYLRU ZDV LGHQWLFDO WR WKH 0Q32 FRPSRXQG IXUWKHU LQGLFDWLQJ WKDW SKRVSKRQDWH ELQGLQJ FDXVHV WKH 6RUHW SHDN DW QP 2&+ 0Q32 LQ VROXWLRQ ZLWK HWKYOSKRVSKRQLF DFLG 7KRXJK WKH DON\O FKDLQV PD\ KDYH DOWHUHG WKH FKURPRSKRUH LQWHUDFWLRQ LQ VROXWLRQ WKH VWURQJHU 89YLV HIIHFWV ZHUH OLNHO\ GXH WR WKH SUHVHQFH RI WKH LQWUDPROHFXODU 5322+f OLJDQGV 7KH ELQGLQJ RI WKH SKRVSKRQLF DFLGV WR WKH FHQWUDO SRUSK\ULQ PHWDO ZDV FRQILUPHG E\

PAGE 104

VWXG\LQJ VROXWLRQV RI 0Q32 [ n 0 LQ &+&f ZLWK HWK\OSKRVSKRQLF DFLG DW KLJK FRQFHQWUDWLRQV ,Q SXUH 0Q32 WKH ;PD[ ZDV REVHUYHG DW QP KRZHYHU ZKHQ [ 0 HWK\OSKRVSKRQLF DFLG ZDV DGGHG D GLVWLQFW EOXH VKRXOGHU EHFDPH YLVLEOH $W HWK\OSKRVSKRQLF DFLG FRQFHQWUDWLRQV DERYH [ 2n 0 RYHU WLPHV WKH SRUSK\ULQ FRQFHQWUDWLRQf WKH GRPLQDQW SHDN ZDV WKH SHDN DW QP )LJXUH f )XUWKHU XSRQ DGGLWLRQ RI SKRVSKRQLF DFLG WR 0Q32 VROXWLRQV LQ &+& DQ REYLRXV SHDN HPHUJHG DW QP %DQG 9D ZDV DEVHQW LQ WKH SXUH 0Q32 VROXWLRQV KHQFH WKLV SHDN ZDV SUREDEO\ UHODWHG WR SKRVSKRQLF DFLG ELQGLQJ L L f§ :DYHOHQJWK QPf )LJXUH 0Q32 LQ &+& [ f 0f ZLWK HWK\OSKRVSKRQLF DFLG Df SXUH 0Q32 Ef [ n 0 HWK\OSKRVSKRQLF DFLG Ff [ n 0 HWK\OSKRVSKRQLF DFLG Gf [ 0 HWK\OSKRVSKRQLF DFLG Hf SXUH 0Q3 7KH SHDN DW QP FRXOG UHSUHVHQW PDQ\ GLIIHUHQW VWDWHV RI WKH SRUSK\ULQ ,W FRXOG EH GXH WR WKH R[LGDWLRQ RI WKH FHQWUDO PHWDO WR D VSLQ VWDWH FRQYHUVLRQ RU HYHQ WR

PAGE 105

GHPHWDOODWLRQ RI WKH PDQJDQHVH SRUSK\ULQ 7KLV SHDN ZDV REVHUYHG LQ WKH DEVHQFH RI DQ\ VWURQJ R[LGDQWV LQGLFDWLQJ WKDW WKLV SHDN LV SUREDEO\ QRW UHSUHVHQWLQJ R[LGDWLRQ SURGXFWV 7KH HOHFWURQLF VSHFWUD RI 0Q,,,f733 &O LQ '062 ZDV SUHVHQWHG E\ +DQVHQ DQG *RII 7KH KLJK VSLQ PRLHW\ WKDW ZDV IRUPHG E\ WKH FRRUGLQDWLRQ RI WKH '062 VROYHQW PROHFXOHV VKRZHG D VKDUS 6RUHW %DQG DW QP ZLWK WZR SURPLQHQW KLJKHU HQHUJ\ EDQGV DW DQG QP +RZHYHU ZKHQ WKH PROHFXOH ZDV FRQYHUWHG WR D ORZVSLQ 0Q,,,fSRUSK\ULQ FRPSOH[ E\ WKH ELVD[LDO OLJDWLRQ RI LPLGD]RODWH DQLRQV WKH 6RUHW %DQG VKLIWHG WR QP DQG EURDGHQHG $OVR WKH EDQG DW QP LQFUHDVHG LQ LQWHQVLW\ ,Q D VLPLODU ZD\ WKH SKRVSKRQLF DFLG RU SKRVSKRQDWH PD\ KDYH EHHQ EHKDYLQJ OLNH WKH LPLGD]RODWH DQLRQ DQG FRQYHUWLQJ WKH 0Q32 IURP D KLJK VSLQ WR D ORZ VSLQ FRPSOH[ 7KH VSLQVWDWH RI 0Q32 LQ VROXWLRQ ZDV VWXGLHG XVLQJ WKH (YDQfV PHWKRG GHVFULEHG LQ &KDSWHU f 7KH 105 UHVXOWV LQGLFDWHG WKDW WKH 0Q32 ZLWK DQG ZLWKRXW SKRVSKRQLF DFLG OLJDQGV ZHUH LQ WKH VDPH VSLQVWDWH WKHUHIRUH WKH REVHUYHG VSHFWUDO EHKDYLRU ZDV GXH RQO\ WR WKH OLJDQG HQYLURQPHQW RI WKH SRUSK\ULQ 7KH SHDN DW QP DOLJQHG ZLWK WKH 6RUHW %DQG RI WKH FRUUHVSRQGLQJ IUHHEDVH SRUSK\ULQ LQ &+& V [ f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

PAGE 106

7KDW VXFK KLJK FRQFHQWUDWLRQV RI HWK\OSKRVSKRQLF DFLG ZHUH QHFHVVDU\ WR LQGXFH D FKDQJH LQ WKH 0Q32 VSHFWUXP LQGLFDWHV WKDW WKH ILYHFRRUGLQDWH 0Q733&Of VWUXFWXUH ZDV JHQHUDOO\ IDYRUHG RYHU WKH VL[FRRUGLQDWH 0Q733&Of3$f VWUXFWXUH 3$ SKRVSKRQLF DFLGf +RZHYHU ZLWK WKH IRXU SKRVSKRQLF DFLGV OLQNHG WR WKH 0Q3 FKURPRSKRUH WKURXJK WKH DON\O FKDLQV WKH HIIHFWLYH FRQFHQWUDWLRQ RI SKRVSKRQLF DFLG LQ WKH YLFLQLW\ RI WKH PHWDO ZDV YHU\ KLJK 7KHUHIRUH 0Q3 LQ &+& VROXWLRQV IDYRU SKRVSKRQLF DFLG D[LDO OLJDWLRQ &RQVLGHULQJ WKH 6RUHW %DQG LQ WKH DERYH 0Q3 FRQFHQWUDWLRQ VWXG\ )LJXUH f LW LV DSSDUHQW WKDW WKLV SUHIHUHQFH LV VWURQJHU LQ WKH PRUH GLOXWH VROXWLRQV RI 0Q3 0Q3 LQ VROXWLRQ ZLWK FKORULGH LRQV ,I WKH 89YLV SHDN DW QP GHPRQVWUDWHG WKH SRUSK\ULQfV SURSHQVLW\ WR ELQG SKRVSKRQLF DFLGV LW ZDV LPSRUWDQW WR GHWHUPLQH LI WKH SKRVSKRQLF DFLG FRXOG EH UHSODFHG ZLWK DQRWKHU OLJDQG VXFK DV LPLGD]ROH ,P+f RU FKORULGH $FFRUGLQJ WR $UDVDVLQJKDP WKH GLVSODFHPHQW RI D ZDWHU RU K\GUR[\ LRQ E\ LPLGD]ROH LV HQFRXUDJHG E\ WKH HOHFWURQGRQDWLQJ QDWXUH RI WKH QLWURJHQ EDVH OLJDQG 8QIRUWXQDWHO\ QR OLWHUDWXUH SUHFHGHQFH ZDV IRXQG RQ WKH VWUHQJWK RI WKH SKRVSKRQDWH ELQGLQJ 7KRXJK FKORULGH ELQGLQJ ZDV LPSOLHG LQ FRQFHQWUDWLRQ VWXGLHV RI 0Q3 LQ &+& LW ZDV IXUWKHU WHVWHG E\ DGGLQJ WHWUD EXW\ODPPRQLXP FKORULGH %X1+ &O WR VROXWLRQV RI 0Q3 DW FRQVWDQW FRQFHQWUDWLRQV RI n DQG n 0 )LJXUH f 6LPLODU EHKDYLRU ZDV REVHUYHG ZLWK DGGHG EURPLGH LRQV ZLWK %DQG 9LL VKLIWHG WR VOLJKWO\ ORZHU HQHUJLHV $V WKH FKORULGH FRQFHQWUDWLRQ LQFUHDVHG WKH UHG VKRXOGHU DW QP VHHQ LQ WKH RULJLQDO 0Q3 VSHFWUD LQ &+& EHFDPH GRPLQDQW DQG WKH EOXH VKRXOGHU LQGLFDWLQJ SKRVSKRQLF DFLG ELQGLQJ GLVDSSHDUHG FRPSOHWHO\

PAGE 107

)LJXUH 6ROXWLRQ 89YLV LQYHVWLJDWLRQ RI 0Q3fV VHQVLWLYLW\ WR GLVSODFHPHQW RI 5 322+f E\ FKORULGH DW [ n 0 &+&f 7KH DUURZV LQGLFDWH WKH FKDQJHV LQ WKH LQWHQVLW\ RI WKH SHDNV DV WKH FKORULGH FRQFHQWUDWLRQ FKDQJHV IURP 0 WR 0 ZKLOH WKH FRQFHQWUDWLRQ RI 0Q3 ZDV FRQVWDQW /DQJPXLU 0RQROD\HUV 7KH PRQROD\HU EHKDYLRU RI 0Q3 ZDV VWXGLHG XVLQJ VXUIDFH SUHVVXUH ,7f YV $UHD 00$f LVRWKHUPV RQ ZDWHU )LJXUH f ,QYHVWLJDWLQJ WKH WLOW DQJOH RI WKH FKURPRSKRUHV WUDQVIHUUHG DW YDULRXV VXUIDFH SUHVVXUHV E\ SRODUL]HG 89YLV JDYH VRPH LQGLFDWLRQ RI WKH FKURPRSKRUH RULHQWDWLRQ LQ WKH PRQROD\HUV 7KH 7$ LVRWKHUP VKRZHG D GLVWLQFW Q RQVHW DW FD ƒ PROHFXOHn +RZHYHU WKH DSSUR[LPDWH DUHD RI WKH FKURPRSKRUH LWVHOI LV FD ƒ PROHFXOHn 7KLV ODUJH RQVHW DUHD LPSOLHG WKDW WKH DON\O FKDLQV ZHUH LQLWLDOO\ EXFNOHG VR ERWK WKH FKURPRSKRUHV DQG WKH SKRVSKRQLF DFLG JURXSV ZHUH VLWWLQJ RQ WKH ZDWHU VXUIDFH 7KH K\GURSKLOLF QDWXUH RI WKH SRUSK\ULQ HVSHFLDOO\ LI WKH WZR D[LDO SRVLWLRQV DUH FRRUGLQDWHG ZLWK ZDWHU PDNHV WKLV D YLDEOH

PAGE 108

VFHQDULR ,Q WKH ILUVW UHJLRQ RI WKH LVRWKHUP nDn RI )LJXUH f WKH FKURPRSKRUHV DQG WKH SKRVSKRQLF DFLGV UHPDLQHG RQ WKH ZDWHU VXUIDFH DQG ZHUH VLPSO\ FRPSUHVVHG )LJXUH ,VRWKHUP RI 0Q3 RQ ZDWHU VXESKDVH 'XULQJ WKH SODWHDX UHJLRQ RI WKH LVRWKHUP nEn RI )LJXUH f WKH FKURPRSKRUHV ZHUH SXVKHG RII WKH ZDWHU VXUIDFH DQG WKH SRUSK\ULQ ULQJV VWDUWHG RYHUODSSLQJ 7KHUH ZHUH OLNHO\ VRPH GLPHUV IRUPLQJ DQG QRW DOO SKRVSKRQLF DFLG HQG JURXSV UHDFKHG WKH VXUIDFH ,Q UHJLRQ fFf RI )LJXUH WKH 00$ ZDV DSSUR[LPDWHO\ ƒ PROHFXOHn LPSO\LQJ WKH SUHVHQFH RI GLPHUV ZKLFK ZHUH WKHQ IXUWKHU FRPSUHVVHG XQWLO WKH fPRQROD\HUf FROODSVHG $W WKLV SRLQW WKH ILOP ZDV OLNHO\ QRW D WUXH PRQROD\HU DV WKH FKURPRSKRUHV HVVHQWLDOO\ IRUPHG D ELOD\HU 7KH VHSDUDWLRQ RI WKH FKURPRSKRUHV IURP WKH ZDWHU VXUIDFH ZDV DFFRPSDQLHG E\ RYHUODSSLQJ ZKLFK ZDV DOVR LQGLFDWHG E\ D FRQVHTXHQW VKLIW LQ WKH PD[ GHWHFWHG E\ UHIOHFWDQFH 89YLV )LJXUH f ,Q UHJLRQ nDn WKH ;PD[ ZDV DW QP :KLOH LQ

PAGE 109

UHJLRQ fEf WKH 6RUHW %DQG VKLIWHG WR DQG UHPDLQHG DW QP 7KH EOXH VKLIW FRUURERUDWHV WKH IRUPDWLRQ RI IDFHWRIDFH GLPHUV 7KH PHDQ PROHFXODU DUHD RI WKLV VSHFWUDO VKLIW LQGLFDWHG WKDW GLPHUV EHJDQ IRUPLQJ HYHQ EHIRUH DOO RI WKH FKURPRSKRUHV ZHUH SXVKHG RII RI WKH ZDWHU VXUIDFH :DYHOHQJWK QPf )LJXUH 5HIOHFWDQFH 89YLV RI 0Q3 RQ ZDWHU VXESKDVH /DQJPXLU%ORGJHWW )LOPV RI SXUH 0Q3 'HSRVLWLRQ RI 0Q3 IURP D SXUH ZDWHU VXESKDVH 8VLQJ WKH /% WHFKQLTXH WKH 0Q3 PRQROD\HUV ZHUH WUDQVIHUUHG DW YDULRXV SRLQWV DORQJ WKH LVRWKHUP 7KH WUDQVPLWWDQFH 89YLV VSHFWUD RI WKHVH ILOPV VKRZHG WKDW WKH EOXH VKLIW LQ WKH ;PD[ IROORZHG WKH VKLIW REVHUYHG LQ WKH UHIOHFWDQFH 89YLV H[SHULPHQWV RQ WKH ZDWHU VXUIDFH )LJXUH f )LOPV WUDQVIHUUHG DURXQG P1 Pn KDG D APD[ DW QP ZKLOH ILOPV WUDQVIHUUHG DW SUHVVXUHV KLJKHU WKDQ P1 Pr ZHUH EOXH VKLIWHG WR QP 7KH 6RUHW %DQG EOXH VKLIW VXJJHVWHG WKDW WKH FKURPRSKRUHV ZHUH LQWHUDFWLQJ DV +W\SH

PAGE 110

DJJUHJDWHV 7KH FKURPRSKRUH LQWHUDFWLRQV REVHUYHG RQ WKH ZDWHU VXUIDFH ZHUH VLPLODU WR WKRVH REVHUYHG LQ WKH GHSRVLWHG ILOPV KRZHYHU WKH DW FD QP DOVR LPSOLHG WKDW WKH FKURPRSKRUHV ZHUH LQWUDPROHFXODUO\ OLJDWLQJ SKRVSKRQLF DFLGV )LJXUH 89YLV RI 0Q3 FDSSLQJ OD\HUV WUDQVIHUUHG RQWR 2'3$=U DW GLIIHUHQW VXUIDFH SUHVVXUHV 7KH SRODUL]HG 89YLV VSHFWUD ZHUH VWXGLHG WR EHWWHU XQGHUVWDQG WKH RULHQWDWLRQ RI WKH FKURPRSKRUHV ZLWKLQ WKH PRQROD\HU ,Q WKH FDVH RI D KLJKVSLQ FRRUGLQDWH 0Q,,,f733 WKH PHWDO W\SLFDOO\ OLHV ZLWKLQ WKH SRUSK\ULQ PDFURPROHFXODU SODQH 7KHUHIRUH WKH WLOW DQJOH RI WKH FKURPRSKRUH ZLWK UHVSHFW WR WKH VXUIDFH FDQ EH GHWHUPLQHG IURP SRODUL]HG 89YLV DV GHVFULEHG LQ &KDSWHU ff :KHQ WKH PRQROD\HU ZDV WUDQVIHUUHG LQ UHJLRQ nDn RI )LJXUH WKH WLOW DQJOH ZDV GHWHUPLQHG WR EH FD r :LWKLQ WKH SODWHDX UHJLRQ RI WKH ,,$ LVRWKHUP WKH WLOW DQJOH LPPHGLDWHO\ DIWHU WUDQVIHU ZDV DV ORZ DV r EXW ZLWKLQ PLQXWHV WKH FKURPRSKRUH UHOD[HG EDFN WR D

PAGE 111

r RULHQWDWLRQ UHODWLYH WR WKH VXUIDFH QRUPDO :KHQ WUDQVIHUUHG DIWHU WKH SODWHDX UHJLRQ DW DUHDV PXFK VPDOOHU WKDQ WKH FKURPRSKRUH LWVHOI WKH WLOW DQJOHV ZHUH FRQVLVWHQWO\ FD r IXUWKHU FRQILUPLQJ WKH SUHVHQFH RI VWDFNHG UDWKHU WKDQ WLOWHG FKURPRSKRUHV 7KH VWDELOLW\ RI ILOPV WUDQVIHUUHG E\ WKH /% WHFKQLTXH EHIRUH GXULQJ DQG DIWHU WKH SODWHDX UHJLRQ RI WKH LVRWKHUP ZHUH WHVWHG E\ H[SRVLQJ WKH ILOPV WR KRW &+& IRU XS WR PLQ HDFK :KHQ WUDQVIHUUHG DW P1 Pn )LJXUH $f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f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

PAGE 112

WKH SKRVSKRQDWH OLJDWLRQ ZDV QRW DV UHYHUVLEOH ZKHQ WKH ILOPV ZHUH WUDQVIHUUHG DW KLJKHU SUHVVXUHV )LJXUH /% ILOPV RI 0Q3 WUDQVIHUUHG DW $f P1P DQG %f P1P ULQVHG LQ &+& :KHQ /% ILOPV RI 0Q3 WUDQVIHUUHG DW ƒ PROHFXOHn P1 Pnf ZHUH ULQVHG RQO\ LQ KRW &+&1 WKH EDQG DW QP %DQG 9LLf ZDV DJDLQ REVHUYHG )LJXUH f 7KH 6RUHW %DQG DW QP FRUUHVSRQGLQJ WR SKRVSKRQDWH ELQGLQJ FRQYHUVHO\ GLVDSSHDUHG 7KHVH UHVXOWV VXJJHVW WKDW KRW VROYHQWV ZHUH DEOH WR HOLPLQDWH WKH SKRVSKRQLF DFLG ELQGLQJ OHDGLQJ WR WKH VWDEOH ILYHFRRUGLQDWH 0Q733&Of VWUXFWXUH DQG WKDW WKH DSSHDUDQFH RI WKLV VWUXFWXUH LV QRW D UHVXOW RI FKURPRSKRUH DJJUHJDWLRQ

PAGE 113

0Q3 WUDQVIHUUHG E\ /% DW P1 Pn DQG ULQVHG LQ &+&1 $f WUDQVIHUUHG IURP D PJ P/n VROXWLRQ 7UDQVIHU RI 0Q3 IURP D FKORULGH LRQFRQWDLQLQJ VXESKDVH ,Q RUGHU WR DYRLG LQWUDPROHFXODU SKRVSKRQLF DFLGPDQJDQHVH ELQGLQJ XSRQ /% WUDQVIHU FKORULGH LRQV ZHUH LQFRUSRUDWHG LQWR WKH VXESKDVH DW D 0 FRQFHQWUDWLRQ 7KH SRUSK\ULQ ZDV VSUHDG DQG FRPSUHVVHG WR P1 Pn IRU WUDQVIHU RQWR D ]LUFRQDWHG 2'3$ WHPSODWH ,Q WKH VSHFWUXP VKRZQ LQ )LJXUH 6RUHW %DQGV ZHUH REVHUYHG DW QP DQG QP &OHDUO\ WKHUH H[LVW GRPDLQV RI ILYHFRRUGLQDWH 0Q733&Of DQG VL[FRRUGLQDWH 0Q733&Of3$f VWUXFWXUHV

PAGE 114

)LJXUH 0Q3 WUDQVIHUUHG IURP 0 >&O @ DTXHRXV VXESKDVH DW P1 P 6HOI$VVHPEOHG ILOPV RI 0Q3 6HOIDVVHPEO\ IURP SXUH VROYHQW 0Q3 ILOPV VHOIDVVHPEOHG IURP (W2++ PL[WXUHf RU &+& VKRZHG D 6RUHW %DQG DW ORZHU HQHUJLHV WKDQ REVHUYHG LQ 0Q3 /% ILOPV 7KH ;PD[ ZDV QRZ DW FD QP ZKLFK FRUUHVSRQGV WR WKH SHDN LQ 0Q3 VROXWLRQV DQG LQ /% ILOPV DIWHU ULQVLQJ RII SK\VLVRUEHG DQG DJJUHJDWHG FKURPRSKRUHV 7KHUHIRUH WKLV SHDN KDV EHHQ DWWULEXWHG WR SKRVSKRQLF DFLG ELQGLQJ WR QRQDJJUHJDWHG PHWDOORSRUSK\ULQV :KHQ VHOIDVVHPEOHG ILOPV RI 0Q3 ZHUH ULQVHG LQ KRW &+& WKH UHG 6RUHW %DQG DVVRFLDWHG ZLWK WKH 0Q733&Of LQFUHDVHG VLJQLILFDQWO\ DQG WKH SHDN DVVRFLDWHG ZLWK WKH VL[FRRUGLQDWH 0Q733&Of3$f GHFUHDVHG DJDLQ SURYLQJ WKDW KRW VROYHQWV FDQ UHPRYH WKH SKRVSKRQLF DFLG OLJDQGV OHDYLQJ WKH FKORULGH OLJDQG LQWDFW

PAGE 115

+RZHYHU WKLV ILYHFRRUGLQDWH VWUXFWXUH ZDV QRW ULJLG :KHQ WKH ILOPV ZHUH OHIW WR VWUXFWXUDOO\ UHOD[ RYHUQLJKW WKH SHDN DW QP GHFUHDVHG LQ LQWHQVLW\ DQG WKH EOXH VKRXOGHU EHFDPH PRUH LQWHQVH 7KLV UHYHUVLEOH EHKDYLRU LQGLFDWHV WKDW WKH OLJDQG HQYLURQPHQW ZKLFK LV YHU\ VHQVLWLYH WR VROYHQW DQG KHDW LV IOH[LEOH )LJXUH f )LJXUH 0Q3 VHOIDVVHPEOHG IURP (W2++ DQG ULQVHG LQ &+& 7KH OHJHQG LQGLFDWHV WKH VSHFWUD DIWHU ULQVLQJ DIWHU EHLQJ OHIW RYHUQLJKW DQG WKH ULQVHG DJDLQ RYHU D WKUHH GD\ SHULRG :KHQ WKHVH ILOPV ZHUH ULQVHG LQ &+&1 EHKDYLRU VLPLODU WR &+& ULQVLQJ ZDV REVHUYHG 7KH EDQG DW QP DJDLQ LQFUHDVHG DQG WKH EDQG DW QP GHFUHDVHG LQ LQWHQVLW\ ZLWK WLPH LQ WKH KRW VROYHQW $JDLQ LI WKH ILOP ZDV OHIW RYHUQLJKW WKH EDQG LQWHQVLWLHV UHYHUVHG )LJXUH f +RW &+&1 WKHUHIRUH DOVR HOLPLQDWHG WKH SKRVSKRQLF DFLG OLJDQG DQG FDXVHG WKH IRUPDWLRQ RI WKH ILYHFRRUGLQDWH 0Q733&Of :KHQ WKH ILOP UHOD[HG WKH SKRVSKRQLF DFLGV KDG D WHQGHQF\ WR ELQG DJDLQ WR WKH FHQWUDO PHWDO IRUPLQJ WKH VL[FRRUGLQDWH 0Q733&Of3$f VWUXFWXUH

PAGE 116

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

PAGE 117

LQFUHDVHG LQ LQWHQVLW\ DQG DUHD %XW LPPHGLDWHO\ DIWHU WKH ILOP ZDV UHPRYHG IURP WKH VROYHQW %DQG 9, GURSSHG OHDYLQJ WKH 99, UDWLR DJDLQ JUHDWHU WKDQ )LJXUH 89YLV UHVSRQVH RI D 6$ 0Q3 ILOP GXULQJ ULQVLQJ ZLWK KRW &+&1 3RODUL]HG 89YLV UHVXOWV ZHUH REWDLQHG IURP WKH VHOIDVVHPEOHG ILOPV RI WKH 0Q3 7KH FKURPRSKRUH WLOW DQJOH ZDV r DW DOO VHOIDVVHPEO\ WLPHV 7KH VHOI DVVHPEO\ RI WKH 0Q3 ZDV IDFLOLWDWHG E\ WKH VWURQJ ELQGLQJ EHWZHHQ WKH ]LUFRQDWHG SKRVSKRQDWH WHPSODWH DQG WKH SKRVSKRQLF DFLGV RQ WKH 0Q3 PROHFXOHV DQG WKH SRVLWLRQ RI WKH SKRVSKRQLF DFLGV RQ WKH SHULSKHU\ RI WKH FKURPRSKRUH OHQGV LW WR OLH IODW LQ WKH ILOPV :KHQ WKH 0Q3 ZDV VHOIDVVHPEOHG RQWR D ]LUFRQDWHG 2'3$ WHPSODWH DQG WKHVH ILOPV ZHUH WKHQ ULQVHG LQ KRW &+& RU &+&1 WKH 6RUHW %DQG FRQYHUVLRQ IURP

PAGE 118

QP WR QP ZDV FRQVLVWHQWO\ REVHUYHG +RZHYHU ZKHQ WKHVH ILOPV ZHUH ULQVHG LQ KRW (W2+ DQ DQRPDO\ RFFXUUHG ,QVWHDG RI WKH LQFUHDVH LQ WKH EDQG DW QP DV ZDV VR FRPPRQO\ REVHUYHG LQ &+& DQG &+&1 QRZ D SHDN WR WKH KLJKHQHUJ\ VLGH RI WKH RULJLQDO EDQG DW QP JUHZ LQ LQWHQVLW\ 7KLV SHDN DOLJQV ZLWK WKH EDQG VHHQ IRU WKH 0Q3 DQG 0Q32 LQ (W2+ VROXWLRQV LQGLFDWLQJ WKDW LQ WKH ILOPV GRPDLQV RI WKH FKURPRSKRUHV ELQG (W2+ DQG WKHUHIRUH H[SHULHQFH PRELOLW\ LQ WKH D[LDO SRVLWLRQV )LJXUH f )LJXUH 89YLV RI 0Q3 VHOIDVVHPEOHG ILOPV EHIRUH DQG DIWHU ULQVLQJ LQ KRW (W2+ 0Q3 6HOIDVVHPEO\ IURP FKORULGH VROXWLRQV 7R DYRLG SKRVSKRQLF DFLG OLJDWLQJ WKH SRUSK\ULQ FHQWUDO PHWDO DQG WR SURPRWH WKH SKRVSKRQLF DFLG ELQGLQJ WR WKH ]LUFRQLXP QHWZRUN WKH 0Q3 ZDV VHOIDVVHPEOHG RXW RI D [ 2n 0 VROXWLRQ RI SRUSK\ULQ WKDW ZDV 0 LQ %X1+ &On )ROORZLQJ D VXFFHVVIXO VHOIDVVHPEO\

PAGE 119

WKH UHVXOWLQJ ILOP ZLOO DSSHDU FRPSOHWHO\ K\GURSKRELF +RZHYHU DIWHU WKH 6$ IURP D FKORULGH FRQWDLQLQJ VROXWLRQ WKH ILOP GLG QRW DSSHDU WRWDOO\ K\GURSKRELF LQGLFDWLQJ D SRWHQWLDOO\ LQFRPSOHWH VHOIDVVHPEO\ +RZHYHU WKH 0Q3 ZDV FOHDUO\ SUHVHQW LQ WKH 89YLV $IWHU ULQVLQJ LQ KRW &+& WKH 6RUHW %DQG DW QP ZDV SUHVHQW ZLWK D GLVWLQFW SHDN DW QP :KHQ WKHVH ILOPV ZHUH VWXGLHG DIWHU D QLJKW LQ WKH GHVLFFDWRU WKH 6RUHW VKRZHG OLWWOH FKDQJH LQ VKDSH 7KLV EHKDYLRU LV FRQVLVWHQW ZLWK D SUHIHUHQFH IRU WKH ILYHFRRUGLQDWH 0Q733&Of DIWHU ULQVLQJ )LJXUH f ,QWHUHVWLQJO\ DIWHU 6$ IURP D FKORULGH FRQWDLQLQJ VROXWLRQ QR SHDN ZDV REVHUYHG DW QP UHSUHVHQWLQJ WKH DEVHQVH RI IUHHEDVH SRUSK\ULQ 7KH H[FHVV FKORULGH SUHVXPDEO\ FRPSHWHV ZLWK WKH OLJDWLRQ RI SKRVSKRQLF DFLGV DQG SUHYHQWV WKHLU LUUHYHUVLEOH ELQGLQJ ZKLFK FRQVHTXHQWO\ SUHYHQWV WKH GHPHWDOODWLRQ RI WKH 0Q733 )LJXUH 0Q3 VHOIDVVHPEOHG IURP D 0 FKORULGH VROXWLRQ

PAGE 120

$V DQ DGGLWLRQDO FRQILUPDWLRQ RI WKH VXFFHVVIXO WHWKHULQJ RI 0Q3 WR WKH ]LUFRQDWHG 2'3$ WHPSODWH ;36 ZDV SHUIRUPHG $ FOHDU SHDN ZDV REVHUYHG IRU )OV 1f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

PAGE 121

DW QP ZKLFK KDV EHHQ DWWULEXWHG WR IRUPDWLRQ RI D VL[FRRUGLQDWH 0Q733&Of3$f VWUXFWXUH $OVR D EDQG DW QP ZDV DVVLJQHG WR %DQG 9, DQG %DQG 9D DW QP ZDV LGHQWLILHG DV FRUUHVSRQGLQJ WR WKH SUHVHQFH RI IUHHEDVH SRUSK\ULQV LQ WKH ILOPV )XUWKHU ULQVLQJ LQ D VROYHQW WKDW FDQ HOLPLQDWH WKH LQWUDPROHFXODU ELQGLQJ RI SKRVSKRQLF DFLG FDXVHV WKH 6RUHW %DQG WR VKLIW WR FD QP UHSUHVHQWLQJ WKH ILYHFRRUGLQDWH 0Q733&Of 7KLV VKLIW LV PRVW SURQRXQFHG LQ VROXWLRQV LQ ZKLFK FKORULGH LRQV KDYH EHHQ DGGHG LQGLFDWLQJ WKDW H[FHVV FKORULGH SUHYHQWV WKH ELQGLQJ RI WKH SKRVSKRQLF DFLG 7KH EDQG UHSUHVHQWLQJ SKRVSKRQLF DFLG ELQGLQJ GHPRQVWUDWHG VRPH UHYHUVLELOLW\ $IWHU ILOPV RI 0Q3 ZHUH ULQVHG LQ &+& RU &+&1 WKH VWUXFWXUH ZDV WKDW RI 0Q733&Of :KHQ WKHVH VDPH ILOPV ZHUH OHIW WR VWUXFWXUDOO\ UHOD[ WKH 89YLV VKRZHG WKH UHDSSHDUDQFH RI WKH EDQG UHSUHVHQWLQJ WKH 0Q733&Of3$f DFFRPSDQLHG E\ D GHFUHDVH LQ WKH LQWHQVLW\ RI WKH 0Q733&Of SHDN :KHQ WKH FKURPRSKRUHV ZHUH DGKHUHG WR WKH ]LUFRQDWHG 2'3$ QHWZRUN E\ OHVV WKDQ IRXU RI WKH SKRVSKRQLF DFLG WHWKHUV WKH QRQERXQG SKRVSKRQLF DFLG JURXSV UHPDLQHG LQ FHQWUDO PHWDOfV YLFLQLW\ 7KHUHIRUH GLVSODFHPHQW RI WKH SKRVSKRQLF DFLG OLJDQGV ZLWK KRW VROYHQWV GRHV QRW SUHYHQW WKHP IURP UHOLJDWLQJ DV WKH ILOP FRQGLWLRQV FKDQJH 7KH 6$ 0Q3 ILOPV KDYH 6RUHW %DQG DEVRUEDQFH LQWHQVLWLHV FRQVLVWHQWO\ EHWZHHQ WR DEVRUEDQFH XQLWV 7KLV DEVRUEDQFH LQWHQVLW\ FRUUHVSRQGV WR WKH /% ILOPV WUDQVIHUUHG DW 00$ MXVW EHIRUH WKH SODWHDX UHJLRQ :KHQ WKH SRUSK\ULQ VXUIDFH FRYHUDJH LV LQFRPSOHWH DV LQ WKH /% ILOPV WUDQVIHUUHG EHORZ P1 Pn DQG LQ WKH ILOPV VHOIDVVHPEOHG IRU YHU\ VKRUW WLPHV WKH DEVRUEDQFH LQWHQVLW\ ZDV FRQVLVWHQWO\ DURXQG RU EHORZ DEVRUEDQFH XQLWV 7KHUHIRUH GHSHQGLQJ RQ WKH GHSRVLWLRQ FRQGLWLRQV WKH DPRXQW RI FKURPRSKRUH LQFRUSRUDWHG LQWR WKH ILOPV LV UHDVRQDEO\ FRQVLVWHQW &RQVLVWHQF\ LQ WKH FKURPRSKRUH ORDGLQJ LV KHOSIXO LQ HPSOR\LQJ WKHVH ILOPV LQ FDWDO\VLV VWXGLHV

PAGE 122

8QIRUWXQDWHO\ WKRXJK WKH 6RUHW %DQG DW $OO QP LV XVXDOO\ DVVRFLDWHG ZLWK FKORULGH ELQGLQJ 6RUHW %DQGV DURXQG QP FDQ EH DVVRFLDWHG ZLWK D QXPEHU RI D[LDO OLJDQGV DQG FKURPRSKRUH LQWHUDFWLRQV PDNLQJ GLIILFXOW DEVROXWH FKDUDFWHUL]DWLRQ RI WKH SRUSK\ULQfV OLJDQG DQG DJJUHJDWLRQ HQYLURQPHQW +RZHYHU XOWLPDWHO\ WKH OLJDQG ILOOLQJ WKH D[LDO SRVLWLRQ RQ WKH FKURPRSKRUH LV OHVV LPSRUWDQW WKDQ LWV ODELOLW\ ,I WKH PHWDO FHQWHU RI WKH SRUSK\ULQ LV DYDLODEOH IRU R[LGDWLRQ WKH FDWDO\VW ZLOO EH DFWLYH $OVR DV ZLOO EH GLVFXVVHG LQ &KDSWHU LI WKH LPLGD]ROH FDQ GLVSODFH WKH D[LDOO\ ERXQG OLJDQG LW FDQ SRVLWLYHO\ LQIOXHQFH WKH FDWDO\VLV

PAGE 123

&+$37(5 ,1&25325$7,21 2) $1 ,0,'$=2/( /,*$1' ,172 0$1*$1(6( 3253+<5,1 &217$,1,1* =,5&21,80 3+263+21$7( 7+,1 ),/06 %DFNJURXQG $V LQ &KDSWHU WKH FKURPRSKRUH FDWDO\VW VWXGLHG ZDV D WHWUDSKHQ\O SRUSK\ULQ SDUDVXEVWLWXWHG ZLWK IRXU RFWDGHF\OSKRVSKRQLF DFLG JURXSV 0Q3f ZKLFK FRXOG WHWKHU WKH SRUSK\ULQ GLUHFWO\ WR WKH ]LUFRQLXP VXUIDFH )RU FRPSDULVRQ WKH PRGHO SRUSK\ULQ 0Q32 ZLWK QR SKRVSKRQLF DFLG FKDLQV ZDV DOVR H[DPLQHG 7KH KHWHURF\FOLF OLJDQG XVHG IRU WKHVH H[SHULPHQWV ZDV DQ DON\OSKRVSKRQLF DFLG LPLGD]ROH ,P2'3$f ZKLFK FRXOG DOVR EH HDVLO\ DWWDFKHG WR WKH ]LUFRQLXP VXUIDFH )URP WKH SURSHQVLW\ RI WKH LPLGD]ROH WR SURWRQDWH LQ WKH SUHVHQFH RI +%U GXULQJ WKH ,P2'3$ V\QWKHVLV WKH LPLGD]ROH XQLW ZDV WKH EURPLGH VDOW XSRQ ILOP SUHSDUDWLRQ )LJXUH f 'HSURWRQDWLRQ RI WKH LPLGD]ROH ZDV DWWHPSWHG LQ RUGHU WR IDFLOLWDWH LWV ELQGLQJ WR WKH PHWDOOR SRUSK\ULQ 7R VWXG\ WKH SRUSK\ULQfV 89YLV VHQVLWLYLW\ WR DQ LPLGD]ROH OLJDQG LQ VROXWLRQ DQ LPLGD]ROH ZLWK QR DON\O FKDLQV ,P+f ZDV DOVR XVHG IRU VROXWLRQ VWXGLHV 7KH DQWLFLSDWHG VWUXFWXUHV RI WKH PL[HG 0Q3,P2'3$ DQG 0Q32,P2'3$ ILOPV DUH VKRZQ LQ VLPSOLILHG IRUP LQ )LJXUH 7KH FKURPRSKRUH LV DW WKH H[WHULRU RI WKH ILOP DQG DYDLODEOH WR FDWDO\]H WKH UHDFWLRQ RI LQWHUHVW 7KH EXON\ FKURPRSKRUH OHDYHV YDFDQW VLWHV DYDLODEOH IRU WKH ,P2'3$ ZKLFK LV WHWKHUHG WR WKH ]LUFRQLXP SKRVSKRQDWH QHWZRUN XQGHU DQG DURXQG WKH FKURPRSKRUH )LJXUH f 0XOWLSOH

PAGE 124

,P2'3$ DUH DQWLFLSDWHG WR EH ORFDWHG EHORZ WKH FKURPRSKRUH SODQH KRZHYHU RQO\ RQH KDV WKH RSSRUWXQLW\ WR ELQG DW D WLPH WR WKH PHWDOORSRUSK\ULQ FRUH )LJXUH 6WUXFWXUHV RI $f 0Q3 %f 0Q32 &f ,P2'3$ DQG 'f ,P+

PAGE 125

,OO k ,P2'3$ )LJXUH 6FKHPDWLF RI 0Q3 DQG ,P2'3$ ILOPV $ YDULHW\ RI PHWKRGV ZHUH HPSOR\HG LQ RUGHU WR DFFRPPRGDWH WKH SRUSK\ULQfV ODUJH 00$ DQG HQFRXUDJH LWV ELQGLQJ WR WKH LPLGD]ROH LQ WKH ILOPV 7KHVH IRUPDWLRQ SURFHGXUHV ZKLFK ZHUH PRWLYDWHG E\ D QXPEHU RI LQWHQWLRQV ZLOO EH GHVFULEHG LQ WKLV FKDSWHU )LUVW WKH 0QSRUSK\ULQLPLGD]ROH ELQGLQJ LV LQ DQ HTXLOLEULXP VWDWH ,Q RUGHU WR HQFRXUDJH WKH LPLGD]ROH ELQGLQJ RU DW OHDVW LWV DYDLODELOLW\ IRU ELQGLQJ WKH LPLGD]ROH KDG WR EH SUHVHQW LQ H[FHVV UHODWLYH WR WKH SRUSK\ULQ 7R LQVXUH H[FHVV LPLGD]ROH WKLV OD\HU ZDV RIWHQ SUHSDUHG ILUVW E\ HLWKHU WKH 6$ RU /% PHWKRG 7KH K\GURSKLOLFLW\ RI ERWK WKH SKRVSKRQLF DFLG DQG WKH LPLGD]ROH FKDLQ WHUPLQDWLQJ JURXSV

PAGE 126

RI WKH ,P2'3$ PDGH WKLV PROHFXOH LPSRVVLEOH WR WUDQVIHU DV SXUH /% ILOPV +RZHYHU WKH ,P2'3$ FRXOG EH PL[HG ZLWK D JRRG ILOPIRUPLQJ PROHFXOH VXFK DV 2'3$ RU +'3$ KH[DGHF\OSKRVSKRQLF DFLGf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f VXEVWLWXWLRQf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

PAGE 127

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f ZDV DGGHG WR D VROXWLRQ RI 0Q32 ZKHUH WKH FRQFHQWUDWLRQ RI WKH 0Q733 ZDV KHOG FRQVWDQW DQG WKH UDWLR RI ,P+0Q733 ZDV LQFUHDVHG :LWK 0Q32 DV DQ H[FHVV

PAGE 128

RI WKH LPLGD]ROH ZDV DGGHG DQ REYLRXV EOXH VKLIW RI DERXW QP WR FD QP ZDV REVHUYHG LQ WKH ;PD[ )LJXUH $f :DYHOHQJWK QPf )LJXUH 6ROYHQW UHVSRQVH RI $f 0Q32 DQG %f 0Q3 WR ,P+ 8SRQ DGGLWLRQ RI ,P+ WR 0Q3 VROXWLRQV LQ &+& WKH RULJLQDO UHG VKRXOGHU RQ WKH 6RUHW %DQG GLVDSSHDUHG DQG ZDV IROORZHG E\ D EOXH VKLIW RI WKH $PD[ WR QP

PAGE 129

)LJXUH %f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

PAGE 130

ZKLFK DJDLQ H[LVW GXH WR DQ LUUHYHUVLEOH ELQGLQJ RI WKH SKRVSKRQLF DFLG WR WKH PDQJDQHVH FHQWUDO PHWDO XQGHU FHUWDLQ FRQGLWLRQV FDXVLQJ WKH GHPHWDOODWLRQ RI WKH 0Q SRUSK\ULQ :DYHOHQJWK QPf )LJXUH 6ROYHQW UHVSRQVH RI $f 0Q32 DQG %f 0Q3 WR ,P2'3$ /HJHQGV LQGLFDWH WKH PRODU UDWLR RI 0Q3 WR ,P2'3$ ,P2'3$ ZDV DOVR DGGHG WR D &+&, VROXWLRQ RI 0Q3 7KH VSHFWUDO EHKDYLRU RI WKLV VROXWLRQ ZDV PRUH XQXVXDO :LWK HT RI ,P2'3$ WKH UHG VKRXOGHU DSSHDUHG

PAGE 131

DW QP DQG WKH EOXH VKRXOGHU DW QP ZDV UHGXFHG LQ DEVRUEDQFH LQWHQVLW\ 7KLV VSHFWUDO EHKDYLRU FRUUHVSRQGV WR VRPH RI WKH SKRVSKRQLF DFLG OLJDQGV EHLQJ GLVSODFHG E\ EURPLGH +RZHYHU WKH EURPLGH OLJDWLRQ GLG QRW DSSHDU WR EH TXDQWLWDWLYH DV ZDV WKH FDVH ZLWK WKH 0Q32 $IWHU WKH DGGLWLRQ RI HT RI WKH ,P2'3$ WKH LQWHQVLW\ RI WKH SHDN DW QP OHYHOHG RII DQG WKH QP SHDN ZDV DW D PLQLPXP :LWK RU PRUH HTXLYDOHQWV RI ,P2'3$ WKH EOXH 6RUHW SHDN RU %DQG 9L VKLIWHG WR QP DQG LQFUHDVHG LQ LQWHQVLW\ )LJXUH f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f,Pf VSHFLHV ZDV SUREDEO\ SUHVHQW LQ VROXWLRQ DW KLJK ,P2'3$ FRQFHQWUDWLRQV ,Q WKH ILOPV RI WKH 0QSRUSK\ULQ WKLV FRPSHWLWLRQ PD\ EH DYRLGHG LI WKH SKRVSKRQLF DFLGV DUH ERXQG WR WKH ]LUFRQDWHG 2'3$ WHPSODWH )LOP 6WXGLHV /DQJPXLU%ORGJHWW )LOPV FRQWDLQLQJ VXEVWLWXWHG 0Q3 0Q3 VXEVWLWXWHG LQWR DQ +'3$ /% ILOP 7R XQGHUVWDQG WKH DELOLW\ RI WKH SRUSK\ULQ WR ELQG WR WKH ]LUFRQLXP QHWZRUN LQ D SUHIRUPHG ELOD\HU D ILOP ZDV SUHSDUHG E\ VXEVWLWXWLQJ D 0Q3 OD\HU LQWR D /% ILOP RI KH[DGHF\OSKRVSKRQLF DFLG +'3$f %\ VXEVWLWXWLQJ WKH SRUSK\ULQ ILOP LQWR DQ DOLSKDWLF FDSSLQJ OD\HU WKH KRSH ZDV WKDW WKH SKRVSKRQLF DFLGV FRXOG VHFXUH WKH SRUSK\ULQ WR WKH VXUIDFH ZKLOH WKH +'3$ ZRXOG EH DEOH WR SUHYHQW SRUSK\ULQ DJJUHJDWLRQ 7KH +'3$ ILOP IRUPHG LQ

PAGE 132

WKLV PDQQHU ZDV ZHOORUJDQL]HG DQG UHSUHVHQWHG WKH PRVW FRPSDFW DQG WKHUHIRUH PRVW FKDOOHQJLQJ ELOD\HU IRU 0Q3 VXEVWLWXWLRQ :LWK WKH SRWHQWLDO SKRVSKRQLF DFLG ELQGLQJ VLWHV LQ WKH =UQHWZRUN RFFXSLHG ZLWK +'3$ WKH SKRVSKRQLF DFLG WHWKHUV RQ WKH SRUSK\ULQ ZHUH DYDLODEOH IRU LQWUDPROHFXODU OLJDWLRQ )URP VROXWLRQ UHVXOWV KRZHYHU FKORULGH RU EURPLGH FRXOG GLVSODFH WKHVH SKRVSKRQLF DFLG D[LDO OLJDQGV )LJXUH f :KHQ WKH VXEVWLWXWHG ILOP ZDV VWXGLHG E\ 89YLV LPPHGLDWHO\ DIWHU WKH 0Q3 6$ SURFHVV ZDV FRPSOHWH WKH DSSHDUHG DW QP $W VXFK D KLJK HQHUJ\ WKH 6RUHW %DQG LPSOLHG WKDW WKH FKURPRSKRUHV ZHUH DJJUHJDWLQJ 7ZR ORZHU HQHUJ\ VKRXOGHUV FRXOG DOVR EH LGHQWLILHG LQ WKH EURDGHQHG 6RUHW %DQG 7KH ILUVW DSSHDUHG DW FD QP ZKLFK PD\ UHSUHVHQW QRQDJJUHJDWHG SRUSK\ULQ GRPDLQV DQG WKH VHFRQG DSSHDUHG DW FD QP DW ORZHU LQWHQVLW\ LQGLFDWLQJ WKH SUHVHQFH RI 0Q733&Of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f3$f SHDN DW QPf RU 0Q733&Of SHDN DW QPf )LJXUH f 'XH WR WKH VSOLWWLQJ DQG EURDGHQLQJ RI WKH 6RUHW %DQG LW LV LPSRVVLEOH WR DWWULEXWH D FKDQJH LQ DEVRUEDQFH LQWHQVLW\ MXVW WR UHPRYDO RI SK\VLVRUEHG FKURPRSKRUHV 6RPH SK\VLVRUEHG FKURPRSKRUHV ZHUH LQGHHG UHPRYHG ZKLFK ZDV IRXQG E\ FDOFXODWLQJ WKH GLIIHUHQFHV LQ SHDN DUHDV EHIRUH DQG DIWHU ULQVLQJ )LJXUH DOVR UHYHDOV D GHFUHDVH LQ WKH DEVRUEDQFH LQWHQVLW\ UDWLR RI %DQG 9 WR %DQG 9, $

PAGE 133

FKDQJH LQ WKH UDWLR RI %DQG 9 WR %DQG 9, LV RIWHQ UHSRUWHGO\ DVVRFLDWHG ZLWK D FKDQJH LQ WKH OLJDQG HQYLURQPHQWf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

PAGE 134

PRQROD\HU IRUPDWLRQ 7KHUHIRUH WKH LPLGD]ROH ZDV GLOXWHG ZLWK +'3$ RU 2'3$ WR DYRLG WKLV SUREOHP $IWHU WKH /% WUDQVIHU RI WKH ,P2'3$+'3$ PL[WXUHV WKH 0Q3 ZDV VXEVWLWXWHG LQWR WKLV OD\HU :KHQ ILOPV FRQWDLQLQJ VROXWLRQV UDQJLQJ IURP b WR b ,P2'3$ LQ +'3$ ZHUH SUHSDUHG DQG WKH 0Q3 ZDV VXEVWLWXWHG LQWR WKHVH ILOPV D SDWWHUQ ZDV REVHUYHG )LJXUH f ,Q WKH ILOPV RI b ,P2'3$ 6$ 0Q3 WKH UDWLR RI 99D ZDV FOHDUO\ OHVV WKDQ 7KLV UDWLR LQFUHDVHG ZLWK DQ LQFUHDVHG FRQFHQWUDWLRQ RI ,P2'3$ %DQG 9D DVVRFLDWHG ZLWK WKH IUHHEDVH SRUSK\ULQ GURSV LQ LQWHQVLW\ ZLWK WKH DGGLWLRQ RI DQ LPLGD]ROH OLJDQG WR FRPSHWH ZLWK WKH SKRVSKRQLF DFLG DV ZDV VHHQ LQ VROXWLRQ VWXGLHV ZLWK 0Q3 DQG ,P+ )LJXUH %f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f 'XH WR WKH VWHULF FRQVWUDLQWV IURP WKH ILOP HQYLURQPHQW LW LV XQOLNHO\ WKDW WKHVH SRUSK\ULQV ZRXOG IRUP ELVLPLGD]ROH FRPSOH[HV >0Q733,Pf@ 7KHUHIRUH WKLV

PAGE 135

SHDN VSOLWWLQJ KDV EHHQ DVVLJQHG WR WKH IRUPDWLRQ RI DV\PPHWULF D[LDOO\ ERXQG SRUSK\ULQV FRH[LVWLQJ ZLWK GRPDLQV RI 0Q733&Of )LJXUH 0Q3 VXEVWLWXWHG RQWR ,P2'3$+'3$ /% ILOPV DIWHU &+& ULQVLQJ 5LQVLQJ LQ KRW &+& VXFFHVVIXOO\ HOLPLQDWHG DQ\ SK\VLVRUEHG FKURPRSKRUHV +RZHYHU KRW &+& KDG D WHQGHQF\ WR DOVR FDXVH D FKDQJH LQ WKH OLJDQG HQYLURQPHQW 7KHUHIRUH URRP WHPSHUDWXUH &+& ZDV H[DPLQHG LQ RUGHU WR HOLPLQDWH WKH SK\VLVRUEHG FKURPRSKRUHV $IWHU ULQVLQJ D b ,P2'3$+'3$ /% ILOP 0Q3 6$ ILOP LQ URRP WHPSHUDWXUH &+& WKH 89YLV VKRZHG EHKDYLRU GLIIHUHQW FRPSDUHG WR KRW &+& 7KH DEVRUEDQFH LQWHQVLW\ RI WKH 6RUHW %DQG GHFUHDVHG DORQJ ZLWK D VKLIW IURP QP WR QP )LJXUH f

PAGE 136

L L L L L n :DYHOHQJWK QPf )LJXUH 0Q3 VXEVWLWXWHG RQWR D b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f

PAGE 137

)LJXUH 89YLV RI DQ ,P2'3$ 0Q3 ILOP DIWHU GU\LQJ 0Q32 OLQNHG WR ,P2'3$ FRQWDLQLQJ /% ILOPV 0Q32 D SRUSK\ULQ ZLWK QR DON\OSKRVSKRQLF DFLG FKDLQV ZDV DVVHPEOHG LQWR ,P2'3$ 6$ ILOPV WR VWXG\ WKH LPLGD]ROH ELQGLQJ LQ D VLPSOLILHG V\VWHP 7KH RQO\ DYDLODEOH PHWKRGV RI DEVRUELQJ 0Q32 WR WKHVH ILOPV ZHUH WKURXJK WKH LPLGD]ROH RU WKURXJK DJJUHJDWLRQ RI FKURPRSKRUHV LH SK\VLVRUSWLRQ WR DOUHDG\ FKHPLVRUEHG SRUSK\ULQV 8SRQ ULQVLQJ DQ\ SK\VLVRUEHG 0Q32fV VKRXOG EH ZDVKHG DZD\ )LJXUH VKRZV WKH 89YLV RI D OD\HU RI 0Q32 DWWDFKHG WR D b ,P2'3$+'3$ /% ILOP 7KH DEVRUEDQFH LQWHQVLW\ RI WKH 0Q32 ILOP ZDV PXFK OHVV WKDQ ILOPV FRQWDLQLQJ WKH 0Q3 EXW WKH SRUSK\ULQ ZDV FOHDUO\ SUHVHQW LQGLFDWLQJ WKH LPLGD]ROH ELQGLQJ ZDV DFWLYH $IWHU PLQ LQ D KRW &+& VROXWLRQ WKH DEVRUEDQFH LQWHQVLW\ RI WKH ILOP GLG GHFUHDVH LQGLFDWLQJ FKURPRSKRUH ORVV +RZHYHU WKH LPLGD]ROH ELQGLQJ ZDV VRPHZKDW VWDEOH WR KRW &+& DV WKH FKURPRSKRUHV ZHUH QRW FRPSOHWHO\ UHPRYHG DIWHU PLQ LQ WKH VROYHQW

PAGE 138

7KH UDWLR RI ,P2'3$ WR +'3$ KDV EHHQ YDULHG DQG 0Q32 ILOPV ZHUH VWLOO VXFFHVVIXOO\ IRUPHG )XUWKHU XVLQJ DQ ,P2'3$2'3$ PL[WXUH LQVWHDG RI ,P2'3$+'3$ DOVR ZRUNHG WR SUHSDUH WKH 0Q32 ILOPV 7KH b ,P2'3$ ILOPV ZHUH VWXGLHG SULPDULO\ EHFDXVH RI WKH EDODQFH RI KLJK LPLGD]ROH ORDGLQJ DQG VWDEOH ILOP EHKDYLRU +'3$ ZDV WKH SULPDU\ GLOXHQW XVHG EHFDXVH LWV FKDLQ OHQJWK ZDV DSSURSULDWH WR IRUP D ILOP ZLWK WKH LPLGD]ROH JURXS IXOO\ H[SRVHG DQG DYDLODEOH IRU ELQGLQJ )LJXUH 0Q32 DWWDFKHG WR D b ,P2'3$+'3$ /% ILOP DQG ULQVHG LQ KRW &+&OM 0QSRUSKYULQV VXEVWLWXWHG LQWR VHOIDVVHPEOHG ILOPV RI ,P2'3$ 89YLV UHVSRQVH RI 0Q3 ILOP WR IEXW\O DPLQH DQG &+&8 ULQVLQJ 0Q3 ZDV VXFFHVVIXOO\ VXEVWLWXWHG LQWR D 6$ OD\HU RI ,P2'3$ $IWHU VXEVWLWXWLRQ WKH ILOPV ZHUH ULQVHG ZLWK D VROXWLRQ RI WEXW\O DPLQH %X1+f WR GHSURWRQDWH WKH LPLGD]ROH DQG IDFLOLWDWH LWV ELQGLQJ WR WKH SRUSK\ULQ 7KH EDVH %X1+ ZDV FKRVHQ

PAGE 139

IRU LWV EXON\ QDWXUH ZKLFK VKRXOG SUHYHQW LWV ELQGLQJ WR WKH SRUSK\ULQ 5LQVLQJ WKH ILOPV LQ %X1+ FDXVHG D EOXH VKLIW LQ WKH 6RUHW %DQG IURP QP WR QP ZKLFK ZDV WKHUHIRUH DVVLJQHG WR LPLGD]ROH ELQGLQJ WR WKH FHQWUDO PHWDO ,W ZDV XQFOHDU LI LPLGD]ROH ELQGLQJ ZDV HQFRXUDJHG E\ GHSURWRQDWLRQ RU LI WKH HOLPLQDWLRQ RI VRPH SK\VLVRUEHG DQG WKHUHIRUH QRQLPLGD]ROH ERXQG SRUSK\ULQV PDGH LW HDVLHU WR REVHUYH WKH LPLGD]ROH ELQGLQJ %HFDXVH RI WKH ILOP VWUXFWXUH WKH FRPSOH[ LV PRVW OLNHO\ D FRRUGLQDWH 0Q733&Of,Pf V\VWHP $IWHU ULQVLQJ ZLWK KRW &+& WKH 6RUHW DEVRUEDQFH LQWHQVLW\ GHFUHDVHG VLJQLILFDQWO\ %DQG 9LL VKLIWHG WR QP ZKLFK ZDV DJDLQ DVVRFLDWHG ZLWK WKH IRUPDWLRQ RI WKH ILYHFRRUGLQDWH 0Q733&Of 7ZHQW\IRXU KRXUV DIWHU ULQVLQJ WKH KDOLGHELQGLQJ SHDN DW QP ZDV QR ORQJHU GHWHFWHG ,QVWHDG WKH EDQG DW QP LQFUHDVHV LQ LQWHQVLW\ DV WKH ILOPV ZHUH OHIW WR UHRUJDQL]H RYHUQLJKW DV ZDV REVHUYHG LQ WKH SXUH 0Q3 ILOPV )URP WKH HQHUJ\ RI WKH EDQG DW QP ZKLFK LV DW ORZHU HQHUJLHV WKDQ WKH 6RUHW %DQG REVHUYHG ZLWK LPLGD]ROH ELQGLQJ WKLV SHDN ZDV OLNHO\ GXH WR WKH ELQGLQJ RI SKRVSKRQLF DFLG OLJDQGV DQG QRW LPLGD]ROHV )LJXUH f 7KH 6RUHW %DQG DEVRUEDQFH LQ WKLV ILOP ZDV FRPSDUDEOH WR WKDW RI SUHYLRXV H[DPSOHV RI SXUH 0Q3 VXEVWLWXWHG LPLGD]ROH ILOPV LPSO\LQJ URXJKO\ WKH VDPH QXPEHU RI FKURPRSKRUHV ZHUH SUHVHQW

PAGE 140

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

PAGE 141

)LJXUH 5HYHUVLELOLW\ RI WKH FKORULGHSKRVSKRQLF DFLG ELQGLQJ 5LQVLQJ WKH VXEVWLWXWHG 0Q3 ILOPV LQ FKORULGH LRQ VROXWLRQV &KORULGH LRQV ZHUH GHOLEHUDWHO\ DGGHG WR WKH V\VWHP E\ ULQVLQJ WKH ILOPV LQ D VROXWLRQ RI WHUW EXW\ODPPRQLXP FKORULGH %X1+ &ff 7KHVH UHVXOWV FRQILUPHG WKDW WKH SHDN DW QP LQ WKH ILOPV UHSUHVHQWHG WKH 0Q733&Of :KHQ WKH 0Q3 VXEVWLWXWHG ILOP ZDV ULQVHG LQ D URRP WHPSHUDWXUH (W2+ VROXWLRQ RI FKORULGH LRQV WKHUH ZDV D FOHDU 6RUHW SHDN VSOLWWLQJ ZLWK WKH UHG SHDN RFFXUULQJ DW QP LQGLFDWLQJ WKDW LQ H[FHVV FKORULGH FDQ ELQG DW URRP WHPSHUDWXUH :KHQ WKLV ILOP ZDV WKHQ SODFHG LQ D URRP WHPSHUDWXUH FKORULGH VROXWLRQ LQ (W2++ WKH 6$ VROYHQW PL[WXUHf %DQG 9LL GLVDSSHDUHG DQG %DQG 9L LQWHQVLILHG )LJXUH f

PAGE 142

)LJXUH 0Q3 VXEVWLWXWHG ILOP ULQVHG LQ FKORULGH DQG WEXW\ODPLQH VROXWLRQV 7R IXUWKHU SURPRWH FKORULGH ELQGLQJ WKH FKORULGHFRQWDLQLQJ (W2++ VROXWLRQV ZHUH KHDWHG +HDWLQJ WKH VROXWLRQ ZRUNHG UHPDUNDEO\ ZHOO DW LQFRUSRUDWLQJ FKORULGH ELQGLQJ DQG WKH ORZ HQHUJ\ SHDN GHYHORSHG VLJQLILFDQWO\ $IWHU EHLQJ OHIW RYHUQLJKW WKH UHG SHDN ZDV PXFK PRUH SHUVLVWHQW 7KLV UHVXOW PD\ LQGLFDWH WKDW LQ WKH

PAGE 143

SUHVHQFH RI D ODUJH H[FHVV RI FKORULGH LRQV FKORULGH ELQGLQJ LV PXFK OHVV PRELOH DQG PRUH GLIILFXOW WR GLVSODFH )LJXUH f 5LQVLQJ LQ %X1+ LQ URRP WHPSHUDWXUH (W2+ FDXVHG WKH FRPSOHWH DQG LPPHGLDWH GLVSODFHPHQW RI WKH FKORULGH OLJDQGV ,W LV NQRZQ WKDW LPLGD]ROHV WHQG WR ELQG PRUH HIILFLHQWO\ WR WKH SRUSK\ULQV WKDQ FKORULGHV DQG VR LW LV SRVVLEOH WKDW WKH EDQG DW QP UHSUHVHQWV LPLGD]ROH ELQGLQJ 3UHSDULQJ WKH VXEVWLWXWHG ILOP IURP D FKORULGH FRQWDLQLQJ VROXWLRQ 7R DYRLG SKRVSKRQLF DFLG ELQGLQJ XSRQ ILOP IRUPDWLRQ D OD\HU RI 0Q3 ZDV DVVHPEOHG IURP D 0 VROXWLRQ RI FKORULGH RQWR DQ ,P2'3$ OD\HU )LJXUH f ,QLWLDOO\ WKH FKORULGH ELQGLQJ ZDV QRW REYLRXV DQG WKH 6RUHW ZDV VOLJKWO\ EOXH VKLIWHG UHODWLYH WR SKRVSKRQLF DFLG ELQGLQJ 6$ 0Q3 :DYHOHQJWK QPf )LJXUH 0Q3 VXEVWLWXWHG IURP D 0 &On VROXWLRQ RQWR DQ ,P2'3$ OD\HU DQG FRPSDUHG WR D 0Q32 VROXWLRQ ZLWK ,P+ ELQGLQJ

PAGE 144

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f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

PAGE 145

)LJXUH ,P2'3$0Q3 VHOIDVVHPEOHG IURP PL[WXUH DQG ULQVHG LQ KRW &+& 2WKHU PHWKRGV IRU SUHSDULQJ ,P2'3$ DQG 0Q3 FRQWDLQLQJ ILOPV /% GHSRVLWLRQ RI 0Q3 IROORZHG E\ VXEVWLWXWLRQ RI ,P2'3$ )LOPV RI 0Q3 ZHUH WUDQVIHUUHG IURP D ZDWHU VXESKDVH DW DQG P1 Pn EHIRUH GXULQJ DQG DIWHU WKH SODWHDX UHJLRQ RI WKH LVRWKHUP VKRZQ LQ )LJXUH f ,P2'3$ ZDV VXEVWLWXWHG LQWR WKHVH ILOPV IURP DQ (W2++ VROXWLRQ ,W ZDV WKRXJKW WKDW LI WKH 0Q3 FRXOG IRUP D FRPSOHWH PRQROD\HU ZLWK SKRVSKRQLF DFLGV ERXQG WR WKH ]LUFRQLXP QHWZRUN SULRU WR LPLGD]ROH EHLQJ SUHVHQW LW PD\ EH PRUH OLNHO\ WKDW WKHUH ZRXOG EH LPLGD]ROH ELQGLQJ LQVWHDG RI SKRVSKRQLF DFLG ELQGLQJ WKH FHQWUDO PHWDO 7KH 89YLV EHKDYLRU RI WKHVH ILOPV DIWHU WKH VXEVWLWXWLRQ RI ,P2'3$ DQG DIWHU ULQVLQJ ZLWK &+& DW URRP WHPSHUDWXUH LV VKRZQ LQ )LJXUH 8QIRUWXQDWHO\ WKHUH DUH

PAGE 146

PDQ\ FRPSOLFDWLRQV ZLWK WKH ILOPV SUHSDUHG LQ WKLV ZD\ )LUVW WKH LPLGD]ROH ZLOO PRVW OLNHO\ ZDQW WR ELQG WR WKH H[SRVHG VXUIDFH RI WKH SRUSK\ULQ ILUVW KRZHYHU WKH SKRVSKRQLF DFLG ZLOO EH WU\LQJ WR EXU\ LQWR WKH ILOP WR ILQG WKH ]LUFRQLXP QHWZRUN )XUWKHU LW LV YHU\ GLIILFXOW WR FRQILUP WKH SUHVHQFH RI WKH LPLGD]ROH LQ WKHVH ILOPV E\ DQ\ PHDQV 7KHUHIRUH WKLV PHWKRG ZDV QRW ULJRURXVO\ SXUVXHG :DYHOHQJWK QPf )LJXUH ,P2'3$ VXEVWLWXWHG LQWR D 0Q3 /% ILOP WUDQVIHUUHG DW P1 Pn /% WUDQVIHU RI PL[HG 0Q3,P2'3$ ILOP DW KLJK S+ )RU FRPSDULVRQ D /% ILOP ZDV SUHSDUHG IURP D VSUHDGLQJ VROXWLRQ FRQWDLQLQJ 0Q3 DQG ,P2'3$ LQ D WR UDWLR ,GHDOO\ D PRQROD\HU ULFKHU LQ ,P2'3$ ZRXOG KDYH EHHQ XVHG EXW DJDLQ WKLV LV D SRRU DPSKLSKLOH IRU /% ILOPV DQG VR WKLV ZDV LPSRVVLEOH 7KHVH ILOPV ZHUH WUDQVIHUUHG DW D YDULHW\ RI SUHVVXUHV DQG S+V ,Q D ILOP WUDQVIHUUHG EHIRUH WKH RQVHW RI WKH LVRWKHUP DW D S+ RI )LJXUH f WKH 6RUHW %DQG DIWHU ZDV DW QP :KHQ WKH ILOP ZDV WUDQVIHUUHG DW D 00$ DVVRFLDWHG ZLWK OLWWOH

PAGE 147

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f )LJXUH /% ILOP RI 0Q3,P2'3$ WUDQVIHUUHG IURP D PL[WXUH RQ DQ DTXHRXV VXESKDVH S+

PAGE 148

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f ,P2'3$ DQG %f 0Q3 VHOIDVVHPEOHG ILOPV 7KH GDVKHG OLQH UHSUHVHQWV WKH *DXVVLDQ SHDN ILW

PAGE 149

7KH OD\HU RI SXUH LPLGD]ROH ZDV VFDQQHG E\ WKH PXOWLSOH[LQJ WHFKQLTXH RYHU WKH QLWURJHQ SHDN 1OVf EHWZHHQ DQG H9 7KH QLWURJHQ SHDN ZKLFK FRXOG RQO\ EH GXH WR WKH SUHVHQFH RI LPLGD]ROH ZDV FOHDUO\ D VLQJOH *DXVVLDQ SHDN FHQWHUHG DW H9 ZLWK D ):+0 RI H9 )LJXUH $f :KHQ D FDSSLQJ OD\HU RI SXUH 0Q3 ZDV VHOIDVVHPEOHG RQWR WKH ]LUFRQDWHG 2'3$ WHPSODWH D QLWURJHQ SHDN ZDV DOVR VHHQ )LJXUH %f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f $OWHUQDWLYHO\ D PL[WXUH RI WKH SRUSK\ULQ DQG LPLGD]ROH LQ D VLPLODU UDWLR ZDV VHOIDVVHPEOHG IURP (W2++ 7KH QLWURJHQ UHJLRQ RI WKHVH VHOIDVVHPEOHG ILOPV VKRZHG WZR SHDNV WKH ILUVW FHQWHUHG DW H9 DQG WKH VHFRQG D EURDGHU SHDN RI DSSUR[LPDWHO\ HTXLYDOHQW LQWHQVLW\ FHQWHUHG DW FD H9 )LJXUH f 7KHVH SHDNV DOLJQ UHDVRQDEO\ ZHOO ZLWK WKRVH RI WKH ;36 VWXGLHV RI WKH SXUH LPLGD]ROH H9f DQG SRUSK\ULQ H9f $JDLQ WKHVH UHVXOWV LQGLFDWH WKH SUHVHQFH RI ERWK WKH LPLGD]ROH DQG WKH SRUSK\ULQ LQ WKHVH VHOIDVVHPEOHG ILOPV 6LPLODU UHVXOWV ZHUH REVHUYHG E\ 2IIRUG HW DO LQ ILOPV RI UXWKHQLXP RU RVPLXP PHWDOORSRUSK\ULQV WKDW ZHUH DGKHUHG WR D 6$ WKLRO

PAGE 150

RQJROG VXUIDFH ;36 WKHUHIRUH FOHDUO\ GHPRQVWUDWHG WKH SUHVHQFH RI ERWK WKH SRUSK\ULQ DQG WKH LPLGD]ROH LQ WKH ILOPV )LJXUH ;36 PXOWLSOH[ VFDQ RI 1OV UHJLRQ RI ,P2'3$0Q3 ILOP VHOI DVVHPEOHG RXW RI &+& VROXWLRQ 7KH GDVKHG OLQHV UHSUHVHQW WKH *DXVVLDQ SHDN ILWV )LJXUH ;36 PXOWLSOH[ VFDQ RI ,P2'3$0Q3 ILOP VHOIDVVHPEOHG IURP D PL[WXUH LQ (W2++ 7KH GDVKHG DQG GRWWHG OLQHV UHSUHVHQW JDXVVLDQ SHDN ILWV

PAGE 151

$75,5 FKDUDFWHUL]DWLRQ RI WKH ILOPV FRQWDLQLQJ VXEVWLWXWHG 0Q3 RQ D VHOIDVVHPEOHG ,P2'3$ OD\HU $Q 2'3$ PRQROD\HU WUDQVIHUUHG E\ WKH /% WHFKQLTXH RQWR D =U2'3$ WHPSODWH OHDGV WR DON\O SHDNV DW FP DQG FPn FRUUHVSRQGLQJ WR WKH YD&+f DQG YV&+f VWUHWFKHV UHVSHFWLYHO\ )RU DON\O FKDLQV LQ D PDMRULW\ WUDPFRQILJXUDWLRQ ZLWK FU\VWDOOLQH RUGHU WKH YD&+f SHDN XVXDOO\ IDOOV EHWZHHQ FQU DQG FPn $ VKLIW WR KLJKHU HQHUJLHV LQGLFDWHV WKH LQWURGXFWLRQ RI GLVRUJDQL]DWLRQ ZLWKLQ WKH K\GURSKRELF UHJLRQ RI WKH ILOP ,Q DGGLWLRQ WKH IXOO ZLGWK DW KDOI PD[LPXP ):+0f RI WKH YD&+f SHDN FDQ EH D PHDVXUH RI WKH SDFNLQJ DQG FRQIRUPDWLRQDO RUGHU ZLWKLQ WKH DON\O UHJLRQ $Q RUJDQL]HG FORVHSDFNHG ILOP KDV D ):+0 RI DSSUR[LPDWHO\ FPn ZKLFK FDQ VWUHWFK WR FPn XSRQ GLVRUJDQL]DWLRQ RI WKH ILOP ,Q ILOPV IRUPHG E\ ERWK WKH /% DQG 6$ RI 2'3$ IURP D (W2++ VROXWLRQ RQWR D ]LUFRQDWHG 2'3$ WHPSODWH WKH YD&+f VWUHWFK FRPHV DW FPn DQG WKH YV&+f LV DW FPn 7KHUHIRUH WKHVH ILOPV DUH PRVWO\ WUDQV DQG FORVH SDFNHG ,Q DGGLWLRQ WKH DEVRUEDQFH LQWHQVLW\ RI WKH YD&+f SHDN LQ WKH FDSSLQJ OD\HU LV EHWZHHQ DQG DX $Q DON\O DEVRUEDQFH LQWHQVLW\ RI WKLV PDJQLWXGH LV WKHUHIRUH DVVRFLDWHG ZLWK WKH IRUPDWLRQ RI D FRPSOHWH RUJDQL]HG PRQROD\HU RI DQ RFWDGHF\O DPSKLSKLOH ,Q RUGHU WR IXUWKHU FRQILUP WKH SUHVHQFH RI LPLGD]ROH LQ WKH ILOPV IRUPHG E\ WKH 6$ RI ,P2'3$ RQWR D ]LUFRQDWHG 2'3$ WHPSODWH WKH YD&+f DQG YV&+f SHDNV ZHUH PRQLWRUHG DQG FRPSDUHG WR WKH $75,5 UHVXOWV REWDLQHG IURP WKH 2'3$ PRQROD\HU 7KH $75,5 VSHFWUD RI WKH ,P2'3$ ILOPV ZHUH UHIHUHQFHG WR WKH ]LUFRQDWHG 2'3$ WHPSODWH WKHUHIRUH ZKDW ZDV SORWWHG ZHUH WKH UHVXOWV IURP MXVW WKH ,P2'3$ FDSSLQJ OD\HU :KHQ WKH =U2'3$ WHPSODWH KDG VRDNHG LQ D (W2++

PAGE 152

VROXWLRQ RI ,P2'3 $ IRU ILYH PLQXWHV WKH DEVRUEDQFH LQWHQVLW\ RI WKH YD&+f SHDN ZDV DX DQG WKH YD&+f DQG YV&+f SHDNV DSSHDUHG DW FPf DQG FP UHVSHFWLYHO\ $IWHU PLQ WKH DEVRUEDQFH LQFUHDVHG WR DX DQG WKH SHDNV VKLIWHG WR FQU DQG FPf 7KHUH ZDV QR IXUWKHU VKLIW REVHUYHG LQ WKHVH SHDNV KRZHYHU WKH DEVRUEDQFH VORZO\ LQFUHDVHG RYHU KU DW ZKLFK WLPH WKH DEVRUEDQFH LQWHQVLW\ UHPDLQHG FRQVWDQW DW DX 7KHVH UHVXOWV SURYHG WKH SUHVHQFH RI D PRQROD\HU RI ,P2'3 $ )LJXUH DQG f +RZHYHU WKH ):+0 RI FPn ZDV VLJQLILFDQWO\ JUHDWHU WKDQ WKRVH VHHQ LQ 2'3$ PRQROD\HUV LQGLFDWLQJ D OHYHO RI GLVRUJDQL]DWLRQ LQ WKHVH VHOIDVVHPEOHG ILOPV $ SHDN ZDV DOVR REVHUYHG DW FPn ZKLFK FRUUHVSRQGV WR WKH SUHVHQFH RI 21 VWUHWFKHV IURP WKH LPLGD]ROH +HQFH $75 ,5 VWXGLHV FRQILUP WKH SUHVHQFH RI D PRQROD\HU RI ,P2'3 $ IRUPHG IURP WKH 6$ RI WKLV DPSKLSKLOH IURP (W2++ )LJXUH $75,5 RI ,P2'3 $ 6$ ILOP

PAGE 153

)LJXUH ,QFUHDVH LQ DEVRUEDQFH LQWHQVLW\ RI FPn SHDN LQ ,P2'3$ ZLWK 6$ WLPH $IWHU D OD\HU RI SXUH ,P2'3$ ZDV IRUPHG D OD\HU RI 0Q3 ZDV VHOI DVVHPEOHG WR PRQLWRU WKH LQFRUSRUDWLRQ RI WKH SRUSK\ULQ LQWR WKHVH ILOPV $IWHU KU WKH DEVRUEDQFH LQWHQVLW\ RI WKH YD&+f SHDN OHYHOHG RII DW DX DV UHIHUHQFHG WR WKH ,P2'3$ PRQROD\HUf EXW WKH SHDN FRQVLVWHQWO\ DSSHDUHG DW FPn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

PAGE 154

SK\VLVRUSWLRQ RI D QXPEHU RI FKURPRSKRUHV LV H[SHFWHG GXH WR WKH SURSHQVLW\ RI WKH SRUSK\ULQV WR DJJUHJDWH +RZHYHU WKLV LPSOLHV D VLJQLILFDQW UHRUJDQL]DWLRQ RI WKH XQGHUO\LQJ LPLGD]ROH PRQROD\HU LQ RUGHU WR KDYH URRP WR LQFRUSRUDWH WKHVH DON\O FKDLQV $IWHU PLQ LQ KRW &+& WKH DEVRUEDQFH LQWHQVLW\ OHYHOHG RII DW DX DQG YD&+f SHDN RFFXUUHG DW FP DV UHIHUHQFHG WR WKH LPLGD]ROH PRQROD\HU )LJXUH $f 7KLV UHVXOW LQGLFDWHV WKDW WKH WUXH SRUSK\ULQ FRQWDLQLQJ PRQROD\HU FRQWDLQV DON\O FKDLQV WKDW DUH GLVRUJDQL]HG DQG LQFOXGH D QXPEHU RI JDXFKH LQWHUDFWLRQV $IWHU UHPRYLQJ WKH SK\VLVRUEHG FKURPRSKRUHV WKH WUXH 0Q3 PRQROD\HU FKDUDFWHULVWLFV ZHUH EHWWHU GHILQHG $OVR WKH 6$ RI WKLV ILOP IRU RQO\ PLQ OHDGLQJ WR DQ DEVRUSWLRQ LQWHQVLW\ RI DX IRUPHG D 6$ ILOP FRQWDLQLQJ DSSUR[LPDWHO\ b RI D FRPSOHWH LPLGD]ROH PRQROD\HU 7KLV LQFRPSOHWH ILOP ZDV WKHQ H[SRVHG WR D 0Q3 VROXWLRQ $IWHU PLQ WKH DEVRUEDQFH LQWHQVLW\ OHYHOHG RII DW DX DQG WKH YD&+f ZDV DW FP $IWHU RQO\ PLQ LQ KRW &+& WKH DEVRUEDQFH GURSSHG GUDVWLFDOO\ WR DX DQG YD&+f VKLIWHG WR FP DV UHIHUHQFHG WR WKH LPLGD]ROH PRQROD\HUf +RZHYHU WKH ,5 VKRZV WKDW WKH 6$ RI D b ,P2'3$ OD\HU UHVXOWHG LQ D UHODWLYHO\ SRRU PRQROD\HU ZKLFK OHIW PDQ\ GHIHFW VLWHV 2ULJLQDOO\ LW ZDV WKRXJKW WKDW WKHVH GHIHFW VLWHV ZRXOG DOORZ IRU WKH PRUH VWUDLJKWIRUZDUG LQFOXVLRQ RI WKH SRUSK\ULQ 8QIRUWXQDWHO\ WKH LPLGD]ROH OD\HU LQ VXFK D VWDWH PD\ EH HDVLO\ UHPRYHG IURP WKH ]LUFRQDWHG 2'3$ WHPSODWH DQG WKH ILQDO ILOP PD\ LQFOXGH OHVV LPLGD]ROH DQG SRUSK\ULQ )LJXUH %f DQG WKHUHIRUH KDYH D ORZHU RYHUDOO DON\O DEVRUEDQFH LQ WKH ,5

PAGE 155

:DYHQXPEHU FPnf :DYHQXPEHU FPnf )LJXUH $75,5 RI DON\O UHJLRQ RI $f 0Q3 VXEVWLWXWHG RQ D b ,P2'3$ EDVH FDSSLQJ OD\HU %f 0Q3 VXEVWLWXWHG RQ D b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

PAGE 156

RI WKH GLIIHUHQW D[LDO OLJDQGV WKH HYLGHQFH LQGLFDWHV WKDW WKH DJJUHJDWLRQ LV SUREDEO\ QRW VLJQLILFDQW LQ WKHVH ILOPV 2ULJLQDOO\ WKH VSHFWUDO FKDQJHV REVHUYHG ZLWK ULQVLQJ ZHUH FRQVLGHUHG GXH WR VRPH FKURPRSKRUH UHRUJDQL]DWLRQ RU SRVVLEOH VROYHQW HIIHFWV +RZHYHU WKH SHDN DW QP DOLJQV ZLWK WKH SRUSK\ULQVf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

PAGE 157

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

PAGE 158

&+$37(5 0$1*$1(6( 3253+<5,1 $1' ,0,'$=2/( &217$,1,1* =,5&21,80 3+263+21$7( 7+,1 ),/06 $6 &$7$/<676 %DFNJURXQG 5HDFWLRQV XVLQJ LPPRELOL]HG FDWDO\VWV KDYH UHFHQWO\ JDLQHG PXFK LQWHUHVW )LUVW WKH LPPRELOL]HG SRUSK\ULQV DUH VRPHZKDW SURWHFWHG IURP GHVWUXFWLYH R[LGDWLRQ EHFDXVH WKH\ DUH LGHDOO\ LVRODWHG IURP RQH DQRWKHU RQ WKH VXUIDFH (OLPLQDWLRQ RI GHVWUXFWLYH R[LGDWLRQ FDQ LPSURYH WKH FDWDO\VWf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fSRUSK\ULQ 0Q7'&33&Off DQG WHWUDNLVSHQWDIOXRURSKHQ\OfSRUSK\ULQ 0Q7)33&Off ZLWK ERWK $f H[FHVV VXEVWUDWH DQG %f H[FHVV R[LGDQW 7KH PRODU UDWLR LQ FRQGLWLRQ $ZLWK 0Q7'&33&Of ZDV F\FORKH[HQH WR LPLGD]ROH WR +2 WR FDWDO\VW DQG XQGHU WKHVH FRQGLWLRQV UHSRUWHG F\FORKH[HQH R[LGH \LHOGV RI b ZHUH REVHUYHG 7KH PRODU UDWLR

PAGE 159

LQYHVWLJDWHG XQGHU FRQGLWLRQ % F\FORKH[HQH WR LPLGD]ROH WR + WR FDWDO\VW ZLWK WKH VDPH SRUSK\ULQ JDYH HSR[LGH \LHOGV RI FD b :KHQ WKH FDWDO\VW ZDV 0Q7)33&Of FDOOHG 0Q32 LQ RXU VWXGLHV WKH \LHOGV ZHUH b XQGHU FRQGLWLRQV $ DQG b XQGHU FRQGLWLRQV % 7KH SRUSK\ULQV FRQWDLQLQJ KDOLGH VXEVWLWXWHQWV RQ WKH SKHQ\O ULQJV DSSHDUHG WR EH IDLUO\ UHVLVWDQW WR EOHDFKLQJ RYHU WKH FRXUVH RI WKH KRPRJHQHRXV UHDFWLRQV %DFLRFFKL HW DO VWXGLHG WKH KRPRJHQHRXV HSR[LGDWLRQ RI F\FORRFWHQH WR F\FORRFWHQH R[LGH XVLQJ ERWK PDQJDQHVH DQG LURQ SRUSK\ULQV DV FDWDO\VWV FRPSDULQJ WKH HIIHFWV RI HOHFWURQ GRQDWLQJ YV HOHFWURQZLWKGUDZLQJ VXEVWLWXHQWV RQ WKH WHWUDSKHQ\O ULQJV 7KH SRUSK\ULQV VWXGLHG LQFOXGHG WHWUDNLV GLPHWKR[\SKHQ\OfSRUSK\ULQ 0Q7'0H233&Off WKH DERYH 0Q7'&3&Of DQG WHWUDSKHQ\OSRUSK\ULQ 0Q733&Off 5HVXOWV LQGLFDWH WKDW 0Q733&Of LQ D UDWLR WR VXEVWUDWH DQG K\GURJHQ SHUR[LGH JDYH HSR[LGH \LHOGV RI b DV UHIHUHQFHG WR WKH LQLWLDO VXEVWUDWH FRQFHQWUDWLRQ 7KH 0Q7'&33&Of GHULYDWLYH LQ WKH VDPH PRODU UDWLR WR VXEVWUDWH DQG R[LGDQW JDYH D b \LHOG DV FRPSDUHG WR b LQ WKH %DWWLRQL UHSRUWf DQG WKH 0Q7'0H233&Of FDWDO\VW JDYH D b \LHOG :KHQ WKH R[LGDQW ZDV LQVWHDG LRGRV\OEHQ]HQH RU 3K,2 WKH VXEVWUDWH ZDV XVHG LQ H[FHVV ZLWK D PRODU UDWLR RI SRUSK\ULQ WR VXEVWUDWH WR 3K,2 UHVSHFWLYHO\ 7KH HSR[LGH \LHOGV UDQJHG IURP WR b ZLWK UHIHUHQFH QRZ WR WKH R[LGDQW ,Q ERWK WKH 3K,2 DQG + HSR[LGDWLRQ UHDFWLRQV WKH EOHDFKLQJ HIIHFWV REVHUYHG ZLWK WKH 0Q7'&33&Of DQG 0Q7'0H233&Of FDWDO\VWV ZHUH PLOG XQGHU b 2QO\ WKH XQVXEVWLWXWHG 0Q733&Of VKRZHG XS WR b EOHDFKLQJ UHSRUWHG RYHU WKH FRXUVH RI WKH KU UHDFWLRQ LQ WKH SUHVHQFH RI 3K,2 7KLQ ILOPV RI FDWDO\WLF SRUSK\ULQV KDYH DOVR EHHQ VWXGLHG $EDWWL HW DO LQYHVWLJDWHG /% ILOPV FRQWDLQLQJ DQ LURQ,,,f WHWUDNLVWHWUDGHF\O1 S\ULG\Of SRUSK\ULQ :LWK WKH LQFOXVLRQ RI DON\O FKDLQV RQ WKH IRXUS\ULGLQH ULQJV FOHDU

PAGE 160

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f WHWUDNLVWHWUDIOXRURSKHQ\O RFWDGHF\OR[\SKRVSKRQLF DFLGfSRUSK\ULQ 0Q3f ZLWK DQG ZLWKRXW LPLGD]ROH RFWDGHF\OSKRVSKRQLF DFLG ,P2'3$f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

PAGE 161

GLFKORUREHQ]HQH VWDQGDUG ZDV XVHG LQ WKH + UHDFWLRQV 7KH VHQVLWLYLW\ IDFWRUV ZHUH FDOFXODWHG XVLQJ (TXDWLRQ :&\22A6 [&\22 ZV$! \22 f DQG ZHUH IRXQG WR EH IRU F\FORRFWHQH R[LGH &\22f DQG IRU F\FORRFWHQH &\&2f ZLWK GHFDQH $IWHU DYHUDJH N YDOXHV ZHUH REWDLQHG IRU WKH &\2 DQG &\22 WKH FDWDO\VLV \LHOGV ZHUH GHWHUPLQHG IURP D *& RI WKH UHDFWLRQ PL[WXUH XVLQJ (TXDWLRQ 7KH DPRXQW RI SURGXFW ZDV FDOFXODWHG LQ JUDPV DQG UHIHUHQFHG WR WKH WKHRUHWLFDO PDVV WR REWDLQ D SHUFHQW \LHOG $Q HPSLULFDO VHQVLWLYLW\ IDFWRU IRU HDFK FRPSRXQG LV QHFHVVDU\ GXH WR WKH IDFW WKDW WKH *& GHWHFWRU GRHV QRW UHVSRQG LGHQWLFDOO\ WR HDFK VROXWH :&\22 ?\22 \22 5HVXOWV f &DWDO\VLV ZLWK 3K,2 DV WKH R[LGDQW 7LPH GHSHQGHQFH RI R[LGDWLRQ \LHOGV $ VWRFN VROXWLRQ RI &\2 DQG 3K,2 ZLWK GHFDQH ZDV SUHSDUHG LQ &+& VROXWLRQ DW D PRODU UDWLR LQ &+& $ P/ DOLTXRW FRQWDLQHG SPRO &\2 SPRO 3K,2 DQG SPRO RI GHFDQH ZKLFK ZDV WKHQ XVHG IRU WKH EODQN UHDFWLRQV ZLWK QR SRUSK\ULQ SUHVHQW &RQVLGHULQJ WKH DPRXQW RI SRUSK\ULQ LQ WKH ILOPV WR EH DSSUR[LPDWHO\ [ n PROHV WKH PRODU UDWLR RI WKH FRUUHVSRQGLQJ KRPRJHQHRXV UHDFWLRQ ZDV LQ DJDLQ P/ RI &+& $OVR FD P/ RI WKH VWRFN VROXWLRQ ZDV LQWURGXFHG LQWR WKH IORZ

PAGE 162

FHOOV FRQWDLQLQJ WKH 0Q3 ILOP 7KH ILOPV XVHG LQ WKHVH H[SHULPHQWV ZHUH SUHSDUHG E\ VHOIDVVHPEOLQJ D PRQROD\HU RI 0Q3 RQWR D ]LUFRQDWHG 2'3$ WHPSODWH DQG ULQVLQJ WKLV WHPSODWH ZLWK KRW &+& 7KH 89YLV EDQG 9D ZKLFK KDV SUHYLRXVO\ EHHQ DVVLJQHG WR WKH IUHHEDVH SRUSK\ULQ LV FOHDUO\ SUHVHQW LQ WKH ILOPV XVHG IRU WKH KU DQG KU H[SHULPHQWV :KHQ WKHVH UHDFWLRQV ZHUH DOORZHG WR SURFHHG RYHU KRXUV *& UHVXOWV LQGLFDWHG WKDW WKH DYHUDJH \LHOG LQ WKH EODQN ZDV FD b LQ WKH KRPRJHQHRXV UHDFWLRQ ZDV b DQG LQ WKH ILOPV EHWZHHQ b DQG b 7KHVH SHUFHQW \LHOGV DV FDOFXODWHG UHODWLYH WR WKH LQWHUQDO VWDQGDUG SHDN ZHUH IDLUO\ FRQVLVWHQW )LJXUH 6$ 0Q3 ILOP EHIRUH DQG DIWHU KU FDWDO\VLV UXQ ZLWK F\FORRFWHQH 3K,2GHFDQH LQ &+& ,QWHUHVWLQJ WR QRWH LV WKH IDFW WKDW HYHQ DIWHU KU LQ WKH FDWDO\VLV UHDFWLRQ WKHUH GRHV QRW DSSHDU WR EH D VLJQLILFDQW EOHDFKLQJ HIIHFW 7KH SRUSK\ULQ DSSHDUV WR VWLOO EH SUHVHQW DQG LQWDFW LQ WKH ILOP :KDW LV QRWLFHDEOH LV WKH IDFW WKDW WKH 6RUHW %DQG

PAGE 163

KDV UHYHUWHG EDFN WR LWV SHDN HQHUJ\ DW QP )URP WKH NQRZQ PHFKDQLVP RI WKLV HSR[LGDWLRQ UHDFWLRQ WKH SRUSK\ULQ ORVHV LWV D[LDO OLJDQG DQG EHFRPHV R[LGL]HG WKHUHIRUH WKHUH LV HYLGHQFH IRU WKLV OLJDQG H[FKDQJH ZKLFK LV ZLWQHVVHG LQ WKH 89YLV RI WKH ILOPV DIWHU WKH FDWDO\VLV )LJXUH f :KHQ WKLV VDPH UHDFWLRQ ZDV UXQ IRU RQO\ KU WKH RYHUDOO \LHOGV DV H[SHFWHG GHFUHDVHG 7DEOH f 7KHVH ILOPV ZHUH SUHSDUHG LQ WKH VDPH PDQQHU DV ZHUH WKH ILOPV VWXGLHG LQ WKH SUHYLRXV FDWDO\VLV H[SHULPHQW 7KH UDWLR RI %DQGV 99, FKDQJHV VOLJKWO\ DV WKH D[LDO OLJDQG HQYLURQPHQW LV QRW LGHQWLFDO LQ ERWK FDVHV $JDLQ WKH 89 YLV EHKDYLRU EHIRUH DQG DIWHU WKH FDWDO\VLV UHDFWLRQ ZDV VWXGLHG DQG LV VKRZQ LQ )LJXUH )LJXUH 6$ 0Q3 ILOP EHIRUH DQG DIWHU KU FDWDO\VLV UXQ ZLWK F\FORRFWHQH 3K,2GHFDQH LQ &+&

PAGE 164

&RQVLGHULQJ WKH RULJLQDO 89YLV VSHFWUD RI WKH ILOPV LQGLFDWHG LQ WKH KU DQG KU H[SHULPHQWV WKHUH DSSHDUHG WR EH D VLJQLILFDQW FRQWULEXWLRQ IURP IUHHEDVH SRUSK\ULQ LQ WKHVH ILOPV )URP WKH VWXGLHV GHVFULEHG LQ &KDSWHU DQG LW ZDV NQRZQ WKDW VHOIDVVHPEOLQJ WKH 0Q3 IURP D VROXWLRQ FRQWDLQLQJ FKORULGH LRQV KHOSHG GLVFRXUDJH WKH SKRVSKRQDWH IURP GHPHWDOODWLQJ WKH SRUSK\ULQ 7R WHVW LI D GHFUHDVH LQ WKH ILOP ORDGLQJ RI IUHHEDVH SRUSK\ULQ DIIHFWHG WKH FDWDO\WLF UHVXOWV D ILOP 6$ IURP D FKORULGH FRQWDLQLQJ VROXWLRQ ZDV HPSOR\HG IRU WKH KU H[SHULPHQW $JDLQ VRPH EOHDFKLQJ RI WKH SRUSK\ULQ ZDV REVHUYHG EXW LW GLG DSSHDU WKDW WKHUH ZDV D VLJQLILFDQW DPRXQW RI WKH RULJLQDO FKURPRSKRUH SUHVHQW DIWHU FDWDO\VLV $OVR WKHUH ZDV QR VLJQLILFDQW FRQWULEXWLRQ IURP IUHHEDVH SRUSK\ULQ WR WKH 89YLV VSHFWUD HYHQ DIWHU WKH FDWDO\VLV UXQ VR WKH FDWDO\VLV GRHV QRW FDXVH WKH 0QSRUSK\ULQ WR GHPHWDOODWH )LJXUH f +RZHYHU WKH HSR[LGH \LHOG ZDV QRW GUDPDWLFDOO\ LPSURYHG E\ HOLPLQDWLQJ WKH IUHHEDVH SRUSK\ULQ IURP WKH ILOPV )LJXUH 89YLV RI 0Q3 ILOP 6$ IURP FKORULGH FRQWDLQLQJ VROXWLRQ XVHG LQ FDWDO\VLV ZLWK 3K,2 DIWHU KU

PAGE 165

7KH EHKDYLRU RI WKH 0Q3 ILOPV LQ WKH HSR[LGDWLRQ UHDFWLRQ ZLWK 3K,2 RYHU KU VKRZHG XS WR D b UHGXFWLRQ LQ WKH DEVRUEDQFH LQWHQVLW\ RI WKH SHDN DW QP 7KH ILOP FRXOG EH UHF\FOHG ZLWK FD D b ORVV LQ FDWDO\WLF DFWLYLW\ EXW FDWDO\VLV FRXOG VWLOO EH REVHUYHG )RU FRPSDULVRQ WKH EOHDFKLQJ RI WKH SRUSK\ULQ LQ WKH KRPRJHQHRXV VROXWLRQ ZDV VWXGLHG )LJXUH f ,W DSSHDUV WKDW DIWHU KU WKHUH ZDV DV PXFK DV D b EOHDFKLQJ RI WKH DFWLYH FKURPRSKRUHV LQ VROXWLRQ $IWHU KU WKH EOHDFKLQJ REVHUYHG ZDV DERXW WKH VDPH DV DW KU 7KH SRUSK\ULQV LPPRELOL]HG LQ WKH ]LUFRQLXP SKRVSKRQDWH ILOPV DSSHDU WR EH VOLJKWO\ PRUH VWDEOH XQGHU PRVW FDWDO\VLV FRQGLWLRQV 7DEOH 7LPH GHSHQGHQFH RI HSR[LGDWLRQ RI F\FORRFWHQH XVLQJ SPRO F\FORRFWHQH DQG SPRO 3K,2 LQ OP/ RI VROXWLRQ 7R WKH KRPRJHQHRXV UHDFWLRQ ZDV DGGHG OQPRO RI 0Q32 ([SHULPHQW &\FORRFWHQH R[LGH
PAGE 166

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

PAGE 167

)LJXUH 0Q3 /% ILOP EHIRUH DQG DIWHU KU FDWDO\VLV UHDFWLRQ 2[LGDWLRQ \LHOG GHSHQGHQFH RQ ILOP SUHSDUDWLRQ PHWKRG 7KH DERYH GHVFULEHG FDWDO\VLV UHVXOWV ZHUH REVHUYHG XVLQJ 0Q3 6$ ILOPV $OWHUQDWLYHO\ SXUH /% ILOPV RI 0Q3 ZHUH DOVR XVHG LQ WKH UHDFWLRQ FHOOV $ 0Q3 ILOP ZDV WUDQVIHUUHG E\ WKH /% WHFKQLTXH DW P1 Pn ZKHUH WKH GHQVLW\ RI FKURPRSKRUHV ZDV KLJK DQG DJJUHJDWLRQ ZDV REVHUYHG 7KH ILOP ZDV ULQVHG WR UHPRYH DQ\ SRVVLEO\ SK\VLVRUEHG FKURPRSKRUHV SUHVHQW GXH WR WKH FRPSUHVVHG QDWXUH RI WKH ILOP 7KHVH ILOPV ZHUH WKHQ XVHG LQ WKH UHDFWLRQ IORZ FHOOV RYHU KU ZLWK D UDWLR RI &\2 WR 3K,2 WR GHFDQH 7KH FRUUHVSRQGLQJ EODQN DQG KRPRJHQHRXV UHDFWLRQV JDYH \LHOGV RI DJDLQ DURXQG b DQG b UHVSHFWLYHO\ KRZHYHU WKH \LHOGV ZLWK WKH ILOPV ZHUH DURXQG b ZKLFK LV VOLJKWO\ ORZHU WKDQ WKDW VHHQ LQ WKH FDVH RI WKH VHOIDVVHPEOHG SRUSK\ULQ

PAGE 168

ILOPV )LJXUH f 7KH ORZHU \LHOG FRXOG EH GXH WR WKH DJJUHJDWHG QDWXUH RI WKH FKURPRSKRUHV UHGXFLQJ WKH DFWLYH SRUSKU\LQ VXUIDFH DUHD 7DEOH &RQYHUVLRQ RI F\FORRFWHQH WR F\FORRFWHQH R[LGH ZLWK SPRO F\FORRFWHQH DQG SPRO 3K,2 LQ OP/ RI VROXWLRQ XVLQJ 0Q3 /% ILOP LQ KU /% 0Q3 &\FORRFWHQH R[LGH
PAGE 169

7DEOH &RQYHUVLRQ RI F\FORRFWHQH WR F\FORRFWHQH R[LGH ZLWK YDU\LQJ F\FORRFWHQH WR 3K,2 UDWLRV LQ OP/ RI VROXWLRQ XVLQJ 0Q3 6$ ILOPV RYHU KU ([SHULPHQW &\FORRFWHQH 2[LGH
PAGE 170

)LJXUH 6$ ,P2'3$6$ 0Q3 VWXGLHG ZLWK 3K,2 IRU HSR[LGDWLRQ RI F\FORRFWHQH 7KH &\22 \LHOGV XVLQJ WKHVH PL[HG ILOPV ZHUH DFWXDOO\ UHGXFHG UHODWLYH WR WKH SXUH SRUSK\ULQ ILOPV ZLWK 3K,2 7KH ORZHU \LHOG FRXOG EH GXH WR D GHFUHDVHG SRUSK\ULQ FRQFHQWUDWLRQ LQ WKH PL[HG ILOPV 7KH 89YLV VSHFWUXP RI WKH ILOPV XVHG IRU WKLV VWXG\ GHPRQVWUDWHG WKDW WKH RYHUDOO DEVRUEDQFH RI WKH 6RUHW %DQG SULRU WR FDWDO\VLV ZDV ORZHU WKDQ WKDW REVHUYHG LQ WKH SXUH SRUSK\ULQ ILOP )LJXUH f 7KLV UHVXOW FRUUHVSRQGHG WR WKH EHKDYLRU RIWHQ REVHUYHG LQ &KDSWHUV ZKHUH SRUSK\ULQ VXEVWLWXWLRQ LQWR D SUHIRUPHG FDSSLQJ OD\HU UHVXOWHG LQ D VOLJKWO\ ORZHU ORDGLQJ WKDQ LQ WKH SXUH VHOIDVVHPEOHG ILOPV

PAGE 171

7DEOH &RQYHUVLRQ RI F\FORRFWHQH WR F\FORRFWHQH R[LGH ZLWK SPRO F\FORRFWHQH DQG SPRO 3K,2 LQ OP/ RI VROXWLRQ DQG LQ ILOPV FRQWDLQLQJ LPLGD]ROH 6$ ,P2'3$6$ 0Q3 )LOP &\FORRFWHQH R[LGH
PAGE 172

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
PAGE 173

&DWDO\VLV XVLQJ )/2R DV WKH R[LGDQW 2[LGDWLRQ ZLWK WLPHV OHVV FDWDO\VW YV RWKHU UHDFWDQWV XPRO ))&) RU SPRO F\FORRFWHQH YV QPRO 0Q3f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‘

PAGE 174

:KHQ H[SHULPHQWV VLPLODU WR WKH %DFFLRFKL VWXG\ ZLWK H[FHVV VXEVWUDWH ZHUH UHSURGXFHG XVLQJ SPRO F\FORRFWHQH DQG SPRO + LQ OP/ RI VROXWLRQ ZLWK SPRO LPLGD]ROH DQG QPRO RI 0Q3 DGGHG WR WKH KRPRJHQHRXV UHDFWLRQ YHU\ OLWWOH HSR[LGH ZDV GHWHFWHG LQ WKH EODQN RU KRPRJHQHRXV UHDFWLRQV )RUWXQDWHO\ D FOHDU LQFUHDVH LQ WKH \LHOG ZDV REVHUYHG ZLWK WKH LPPRELOL]HG SRUSK\ULQV 7DEOH f $V LQ WKH 3K,2 UHDFWLRQV WKH LPPRELOL]HG FDWDO\VW DSSHDUHG WR EH UHODWLYHO\ VWDEOH WRZDUG WKH UHDFWLRQ FRQGLWLRQV )LJXUH f 7DEOH &RQYHUVLRQ RI F\FORRFWHQH WR F\FORRFWHQH R[LGH ZLWK SPRO F\FORRFWHQH DQG SPRO + LQ OP/ RI VROXWLRQ XVLQJ LPLGD]ROH DQG SRUSK\ULQ 6$ ,P2'3$6$ 0Q3 &\FORRFWHQH R[LGH
PAGE 175

)LJXUH 6$ ,P2'3$6$ 0Q3 DIWHU ULQVLQJ DQG DIWHU KU LQ FDWDO\VLV UHDFWLRQ ZLWK H[FHVV + $OVR WKH HSR[LGH \LHOG ZLWK WKH ILOP ZDV QRZ DURXQG b f§ QHDUO\ LGHQWLFDO WR WKDW VHHQ LQ WKH KRPRJHQHRXV DQG EODQN UHDFWLRQV UXQ LQ YLDOV ,QWHUHVWLQJO\ ZKHQ WKLV UHDFWLRQ ZDV UXQ LQ D YLDO ZLWK SPRO RI 0Q32 PLPLFNLQJ WKH OLWHUDWXUH SURFHGXUH WKH \LHOG ZDV b FORVHO\ UHVHPEOLQJ WKH \LHOG UHSRUWHG ZLWK D 0Q7)33 &O FDWDO\VW 2[LGDWLRQ ZLWK WLPHV OHVV FDWDO\VW YV RWKHU UHDFWDQWV W XPRO ))2 RU XPRO FYFORRFWHQH YVO QPRO 0Q3N %HFDXVH WKH HSR[LGH \LHOG LQ WKH DERYH UHDFWLRQV PD\ EH ORZHU WKDQ XVXDO GXH WR WKH YHU\ VPDOO DPRXQW RI FDWDO\VW SUHVHQW UHODWLYH WR UHDFWDQWV DQ DWWHPSW ZDV PDGH WR EULQJ WKHVH FRQFHQWUDWLRQV FORVHU WR WKH OLWHUDWXUH UDWLRV RI UHDFWDQW WR FDWDO\VW $GGLWLRQDOO\ WKLV R[LGDQW FRQFHQWUDWLRQ SPRO YV QPRO FDWDO\VWf FOHDUO\ FDXVHV WKH GHJUDGDWLRQ RI WKH SRUSK\ULQ ILOPV

PAGE 176

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f ,Q DGGLWLRQ WKH HSR[LGH \LHOG ZLWK WKH LPPRELOL]HG FDWDO\VW XQGHU WKHVH FRQGLWLRQV ZDV VLPLODU WR RU OHVV WKDQ WKDW REVHUYHG LQ WKH KRPRJHQHRXV FDVH 7KH UHDVRQV EHKLQG WKHVH UHVXOWV DUH QRW FOHDU

PAGE 177

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

PAGE 178

5()(5(1&(6 f 3DSNRYVN\ % 6HQVRUV DQG $FWV % &KHP f -XQJ < 3HDUVRQ & .LOLW]LUDNL 0 +RUVEXUJK /( 0RQNPDQ $3 6DPXHO ,': 3HWW\ 0& 0DWHU &KHP f 2JDWD 1 0DNURPRO &KHP0DFURPRO 6\PS f 3DSNRYVN\ % 2YFKLQLNRY $1 3RQRPDUHY *9 .RUSHOD 7 $QDO /HWW f )DELDQRZVNL : -DFFRGLQH 5 .RGQDQL 5 3HDUVRQ 5 6PHNWDOD 3 $GY 0DW 2SW (OHF f 3DSNRYVN\ % 'HV\DWHULN ,9 3RQRPDUHY *9 .XURFKNLQ ,1 .RUSHOD 7 $QDO&KLP$FWD f $UDPDNL &RUURVLRQ 6FL f $UQROG 3 0DQQR 0LFRFFL 6HUUD $ 7HSRUH $ 9DOOL / 7KLQ 6ROLG )LOPV f 3HQ]D 0 0LOHOOD ( $QLVLPNLQ 9, ,((( 7 8OWUDVRQ )HUU f .DXIIPDQ ) +RIIPDQ % (UEDFK 5 +HLOLJHU / 6LHJPXQG +8 9RONHU 0 6HQVRUV DQG $FWV %FKHPLFDO f 0DUORZ $ / 'DYLV -7 7HW /HWW f 3HWUXFFL 0 / .DNNDU $ &KHP 0DWHU f 6XK +f +RQJ 6+ $P &KHP 6RF f $JDUZDO 9 3K\VLFV 7RGD\ f 5REHUWV * /DQJPXLU%ORGJHWW )LOPVn 3OHQXP 3UHVV 1HZ
PAGE 179

f %DUWHOO / 6 5XFK 53K\V &KHP f 8OPDQ $ $Q ,QWURGXFWLRQ WR 8OWUDWKLQ 2UJDQLF )LOPV )URP /DQJPXLU %ORGJHWW WR 6HOI$VVHPEO\ $FDGHPLF 3UHVV %RVWRQ f =DVDG]LQVNL $ 9LVZDQDWKDQ 5 0DGVHQ / *DPDHV 6FKZDUW] 6FLHQFH f *DLQHV ,QVROXEOH 0RQROD\HUV DW /LTXLG*DV ,QWHUIDFHVn :LOH\ ,QWHUVFLHQFH 1HZ
PAGE 180

f %\UG + 3LNH 7DOKDP 5 6\Q 0HW f 6HLS & 7 %\UG + 3LNH :KLSSV 6 7DOKDP 5 ,Q 3K\VLFDO 6XSUDPROHFXODU &KHPLVWU\ (FKHJR\HQ / .DLIHU $ ( (GV 9RO f 6HLS & 7 %\UG + 7DOKDP 5 ,QRUJ &KHP f 6HLS & 7 *UDQURWK ( 0HLVHO 0 : 7DOKDP 5 $P &KHP 6RF f &OHDUILHOG $ &KHP 0DWHU f &HPWR 7ULILUR ) (EQHU -5 )UDQFKHWWL 90 &KHP 5HY f )ULQN :DQJ 5& &ROQ / &OHDUILHOG $ ,QRUJDQLF &KHPLVWU\ f &DR 0DOORXN 7 ( ,QRUJDQLF &KHPLVWU\ f &DR /\QFK 9 0
PAGE 181

f :DQJ 5& =KDQJ < +X + )UDXVWR 5 5 &OHDUILHOG $ &KHP 0DWHU f 7KRPDV / & &KLWWHQGHQ 5 $ 6SHFWURFKLPLFD $FWD $ f /HH + .HSOH\ / +RQJ +* 0DOORXN 7 ( $P &KHP 6RF f /HH + .HSOH\ / +RQJ +* $NKWHU 6 0DOORXN 7 ( 3K\V &KHP f &DR +RQJ +* 0DOORXN 7 ( $FF &KHP 5HV f )DQXFFL ( 6HLS & 7 3HWUXVND 0 $ 5DYDLQH 6 1L[RQ & 0 7DOKDP 5 7KLQ 6ROLG )LOPV f 3HWUXVND 0 $ )DQXFFL ( 7DOKDP 5 &KHP 0DWHU f )DQXFFL ( 3HWUXVND 0 $ 0HLVHO 0 : 7DOKDP 5 6ROLG 6WDWH &KHP f 3HWUXVND 0 $ 7DOKDP 5 &KHP 0DWHU f &URQH\ & +HOPV 0. -DPHVRQ '0 /DUVHQ 5: 3K\V &KHP % f +VLDR -6 .UXHJHU %3 :DJQHU 5: -RKQVRQ 7( 'HODQH\ -. 0DX]HUDOO '& )OHPLQJ *5 /LQGVH\ -6 %RFLDQ ') 'RQRKRH 5$P &KHP 6RF f ,VKLGD $ 6DNDWD < 0DMLPD 7 &KHP /HWW f -ROOLIIH %HOO 7 *KLJJLQR /DQJIRUG 6 3DGGRQ5RZ 0 $QJHZ &KHP ,QW ( f )ORUVKHLPHU 0 0RKZDOG + 7KLQ 6ROLG )LOPV f $PLQL 0 6KDKURNKLDQ 6 7DQJHVWDQLQHMDG 6 $QDO\VW f $UQROG 0DQQR 0LFRFFL $ 7HSRUH $ 9DOOL / /DQJPXLU f 6PLWK 9 & %DWW\ 69 5LFKDUGVRQ 7 )RVWHU .$ -RKQVWRQH 5$: 6REUDO $-)1 5RFKD *RQ]DOHV $0Gn$ 7KLQ 6ROLG )LOPV f 6FKHQQLQJ $ +XEHUW )HWWHUV 0 1ROWH 5 /DQJPXLU

PAGE 182

f /DKLUL )DWH *' 8QJDVKH 6% *URYHV -7 $P &KHP 6RF f 6FKHQQLQJ $ 3 + /XWMH 6SHOEHUJ -+ 'ULHVVHQ 0&3) +DXVHU 0-% )HLWHUV 0& 1ROWH 5-0 $P &KHP 6RF f 7KH 3RUSK\ULQVn 'ROSKLQ $FDGHPLF 3UHVV 1HZ
PAGE 183

f 0RKDMHU 'f 0RQIDUHG ++ &KHP 5HV 6 f $UDVDVLQJKDP 5 +H *; %UXLFH 7& $P &KHP 6RF f $UDVDVLQJKDP 5 6 %UXLFH 7& $P &KHP 6RF f %DFLRFFKL ( %RVFKL 7 *DOOL & /DSL $ 7DJOLDWHVWD 3 7HWUDKHGURQ f *XR && /L +3 ;X -% &DW f &ROLPDQ 3 =KDQJ ; /HH 98IIHOPDQ (6 %UDXPDQ -, 6FLHQFH f /DL 76 .ZRQJ +/ &KH &0 3HQJ 60 &KHP &RPPXQ f *LOPDUWHQ & /LQGVD\ 6PLWK &KHP 6RF 3HUNLQ 7UDQV f 0LNL 6DWR < %XOO &KHP 6RF -SQ f 'HQLDXG 6FKROORP % 0DQVX\ 5RX[HO %DWWLRQL 3 %XMROL % &KHP 0DWHU f 0DUWLQH]/RUHQWH 0 $ %DWWLRQL 3 .OHHPLVV : %DUWROL -) 0DQVX\ 0RO &DW $ f &RRNH 3 5 /LQGVD\ 6PLWK -5 7HW /HWW f 1H\V 3 ( ) 6HYHUH\QV $ 9DQNHOHFRP ,)&HXOHPDQV ( 'HKDHQ : -DFREV 3$ 0RO &DW $ &KHPLFDO f *URYHV 7 8QJDVKH 6% $P &KHP 6RF f &DPSHVWULQL 6 0HXQLHU % ,QRUJ &KHP f
PAGE 184

f %DWWLRQL 3 5HQDXG -3 %DUWROL -) 5HLQD$UWLOHV 0 )RUW 0 0DQVX\ $P &KHP6RF f .HUQ : (OHFWURFKHP 6RF f $GYLQFXOD 5 'LVVHUWDWLRQ 8QLYHUVLW\ RI )ORULGD f (YDQV ) &KHP 6RF f 6FKXEHUW ( 0 &KHP (G f 6DOW]PDQ + 6KDUHINLQ -* 2UJDQLF 6\QWKHVLV f /XFDV + .HQQHG\ (5 2UJDQLF 6\QWKHVLV &ROO 9RO f 0RQWDQDUL ) 0HWDOORSRUSK\ULQV &DWDO\VHG 2[LGDWLRQV .OXZHU $FDGHPLF 3XEOLVKHUV f &DXJKH\ : 'HDO 5 :HLVV & *RXWHUPDQQ 0 0RO 6SHF f 7DOKDP 5 6HLS & 7 :KLSSV 6 )DQXFFL ( 3HWUXVND 0 $ %\UG + &RPPHQWV ,QRUJ &KHP f 3HWUXVND 0 $ 7DOKDP '5 /DQJPXLU VXEPLWWHG f 'D\ 9 : 6WXEV %5 7DVVHW (/ 'D\ 52 0DULDQHOOL 56 $P &KHP 6RF f 7XOLQVN\ $ &KHQ %0/ $P &KHP 6RF f +DQVHQ $ 3 *RII +0 ,QRUJ &KHP f 6FKDUGW % & +ROODQGHU )+LOO &/ $P &KHP 6RF f %RXFKHU / $P &KHP 6RF f 3RZHOO 0 ) 3DL () %UXLFH 7& $P &KHP 6RF f 0X ; + 6FKXOW] )$ ,QRUJ &KHP f 0DLWL 1 & 0D]XPGDU 6 3HULDVDP\ 1 3K\V &KHP % f 1L[RQ & 0 &ODLUH / 2GREHO ) %XMROL % 7DOKDP 5 &KHP 0DWHU

PAGE 185

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fV JURXS LQ WKH VSULQJ RI MXVW LQ WLPH WR GR KHU RUDO TXDOLI\LQJ H[DP 6KH PDUULHG /DZUHQFH /HH LQ -XO\ RI DQG ZLOO EH MRLQLQJ KLP LQ 1HZ
PAGE 186

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r FHUWLI\ WKDW KDYH UHDG WKLV VWXG\ DQG WKDW LQ P\ RSLQLRQ LW FRQIRUPV WR DFFHSWDEOH VWDQGDUGV RI VFKRODUO\ SUHVHQWDWLRQ DQG LV IXOO\ DGHTXDWH LQ VFRSH DQG TXDOLW\ DV D GLVVHUWDWLRQ IRU WKH GHJUHH RI 'RFWRU RI 3KLORVRSK\ A f§ 0DUWLQ 9DOD 3URIHVVRU RI &KHPLVWU\ FHUWLI\ WKDW KDYH UHDG WKLV VWXG\ DQG WKDW LQ P\ RSLQLRQ LW FRQIRUPV WR DFFHSWDEOH VWDQGDUGV RI VFKRODUO\ SUHVHQWDWLRQ DQG LV IXOO\ DGHTXDWH LQ VFRSH DQG TXDOLW\ DV D GLVVHUWDWLRQ IRU WKH GHJUHH RI 'RFWRU RI 3KLORVRSK\ ILW £af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


53
spread and transferred at 3 mm min'1 on the upstroke forming the ODPA/Zr/30:70
MnP4:ImODPA films.
For the self-assembly of the imidazole onto a zirconated ODPA template, 2 mL
of a 0.5 mg mL'1 solution of ImODPA in EtOH was dissolved in a 9/1 EtOH/H20
mixture in a 50 mL vial. The substrate containing the zirconated ODPA template was
placed in the vial and the film was allowed to self-assemble for 2 hr. When the self-
assembly procedure was complete, the film was rinsed with nanopure water and dried
with forced air. The MnP4 molecules were allowed to substitute into these films as
described in section 2.3.2. Similarly, mixed MnP4 and ImODPA solutions were
prepared at a variety of ratios in EtOH/H20, and the mixed monolayer was allowed to
self-assemble for 2 hr.
The ImODPA was deprotonated as mentioned in Chapter 5 by soaking the
mixed film in an EtOH solution containing /-butyl amine. The /-butyl amine was used
to deprotonate the imidazole within the films so the ligand would be available for
binding the central manganese. The concentration of this solution was not precise but
was consistently ca. 0.1 M and rinsing times were ca. 15 min.
2.3 Catalysis
2.3.1. Catalysis using PhIO as an oxidant
Pure porphyrin films behaved as catalysts for the epoxidation of cyclooctene
using iodosylbenzene (PhIO) as the oxidant. PhIO was synthesized from the diacetate
precursor using NaOH.121 Iodobenzene diacetate (3.0 g, 9.3 mmol) was placed in an
Erlenmeyer flask. 30 mL of 3 N NaOH was added with stirring over 5 min. The
mixture was stirred for 15 min and left to sit uncovered 45 min. 100 mL deionized
H20 was added with stirring and the yellow solid was filtered using a Buchner funnel.


168
(77) Lahiri, J., Fate, G.D., Ungashe, S.B., Groves, J.T. J. Am. Chem. Soc. 1996,
118, 2347-2358.
(78) Schenning, A. P. H. J., Lutje Spelberg, J.H., Driessen, M.C.PF., Hauser,
M.J.B., Feiters, M.C., Nolte, R.J.M. J Am. Chem. Soc. 1995,117, 12655-
12656.
(79) The Porphyrins', Dolphin D. Academic Press: New York, 1978; Vol. IA.
(80) The Porphyrins', Gouterman, M., Dolphin D. Ed.; Academic Press: New York,
San Francisco, London, 1978; Vol. III.
(81) Gouterman, M. J. Mol. Spec. 1961, 6, 138-163.
(82) Kroon, J. M., Koehorst, R.B.M., van Dijk, M., Sanders, G.M., Sudholter,
E.J.R. J. Mater. Chem. 1997, 7, 615-624.
(83) The Porphyrins', Academic Press: New York, 1978; Vol V.
(84) Kroon, J.; Sudholter, E.; Schenning, A.; Nolte, R. Langmuir 1995,11, 214-
220.
(85) Zhang, J.; Wang, D.; Chen, Y.; Li, T.; Mao, H.; Tian, H.; Zhou, Q.; Xu, H.
Thin Solid Films 1997, 300, 208-212.
(86) Gregory, B. W., Vaknin, D., Gray, J.D., Ocko, B.M., Stroeve, P., Cotton, T.M.,
Struve, W.S. J. Phys. Chem. B 1997,101, 2006-2019.
(87) Tour, J. M., Jones, LeRoy III, Pearson, D.L., Lamba, J.J.S., Burgin, T.P.,
Whitesides, G.M., Aliara, D.L., Parikh, A.N., Atre, S.V. J. Am. Chem. Soc.
1995,117, 9529-9534.
(88) Abatti, D.; Zaniquelli, M. E.; Iamamoto, Y.; Idemori, Y. Thin Solid Films
1997, 310, 296-302.
(89) Anikin, M.; Tkachenko, N.; Lemmetyinen, H. Langmuir 1997,13, 3002-3008.
(90) Honeyboume, C.; Barrell, K. J. Mater. Chem. 1996, 6, 323-329.
(91) Ruaudel-Teixier, A.; Barraud, A.; Belbeoch, B.; Roulliay, M. Thin Solid Films
1983, 99, 33-40.
(92) Song, X.; Miura, M.; Xu, X.; Taylor, K.; Majumder, S.; Hobbs, J.; Cesarano,
J.; Shelnutt, J. Langmuir 1996, 12, 2019-2027.
(93) Breslow, R., Zhang, X., Huang, Y. J. Am. Chem. Soc. 1997,119, 4535-4536.
(94) Robert, A., Loock, B., Momenteau, M., Meunier, B. Inorg. Chem. 1991, 30,
706-711.
(95) Beck, M. J., Gopinath, E., Bruice, T.C. J. Am. Chem. Soc. 1993,115, 21-29.


133
chromophore aggregation, the Soret Band at 459 nm possibly corresponds to
imidazole binding. The basic subphase was intended to deprotonate the imidazole
and encourage its binding to the porphyrin while reducing the porphyrin aggregation,
as seen in the case of the Pd-porphyrins in Chapter 3. Additionally, the basic subphase
would deprotonate the phosphonic acids causing them to be even more hydrophilic
and more likely to be on the water surface. Unfortunately, it is very difficult to
confirm the presence or binding of the imidazole in these films. XPS scans of the N]s
region were not helpful in determining if there were two nitrogen environments
present; therefore, these films were not a major focus for the preparation of catalytic
films.
Wavelength (nm)
Figure 5.16: LB film of MnP4/ImODPA transferred from a 25/75 mixture on an
aqueous subphase, pH 11.3.


48
2.2 Porphyrin Films
2.2.1. Palladium Porphyrin Films
The palladium porphyrins studied were palladium 5,10,15,20-tetrakis(2,3,5,6-
tetrafluorophenyl-4-octadecyloxyphosphonic acid)porphyrin (PdP4) and palladium
5,10,15-tris(2,6-dichlorophenyl)-20- (2,3,5,6-tetrafluorophenyl-4-
octadecyloxyphosphonic acid)porphyrin (PdPl). The Bujoli group provided us with
these porphyrin amphiphiles.
The Pd-porphyrins made well-behaved monolayers; therefore, these
amphiphiles were often transferred by the LB technique. Additionally, the Pd-
porphyrins were studied in diluted mixtures with ODPA in an attempt to disrupt the
aggregate formation in the films. For mixed, Pd-porphyrin/ODPA films, the two
materials were simultaneously dissolved in a CHC13 solution. The weighted average
concentration and molecular weight were calculated and used in the KSV software to
monitor the MMA with compression. Ratios of PdP (1 and 4) to ODPA studied
included 1:0, 1:1,1:4, 1:9 and 0:1, respectively.
The creep of the pure palladium-porphyrin Langmuir monolayers was studied
at high and low pressures over 30 min, or slightly longer than the time of one
deposition. At a constant pressure of 12 15 mN nr1, the area changed by 6% and
12% for PdP4 and PdP 1, respectively. At low pressure (3-5 mN nr1), the change in
area was 3% and 7% for PdP4 and PdPl, respectively. The instability in the
monolayers led to a necessary correction in the transfer ratios. The corrected transfer
ratios for the pure PdP4 were 1.0-1.4 at high pressures and 1.0- 1.1 at low pressures.
For the pure PdPl, the corrected transfer ratios were 0.8 1.0 and 0.9 1.0 for high


105
the resulting film will appear completely hydrophobic. However, after the SA from a
chloride containing solution, the film did not appear totally hydrophobic indicating a
potentially incomplete self-assembly. However, the MnP4 was clearly present in the
UV-vis. After rinsing in hot CHC13, the Soret Band at 475 nm was present with a
distinct peak at 460 nm. When these films were studied after a night in the desiccator,
the Soret showed little change in shape. This behavior is consistent with a preference
for the five-coordinate MnTPP(Cl) after rinsing (Figure 4.17). Interestingly, after SA
from a chloride containing solution, no peak was observed at 418 nm representing the
absense of free-base porphyrin. The excess chloride presumably competes with the
ligation of phosphonic acids and prevents their irreversible binding, which
consequently prevents the demetallation of the MnTPP.
Figure 4.17: MnP4 self-assembled from a 0.1 M chloride solution.


64
115 2 molecule-1. The MM A of the tetraphenyl porphyrin is 200 2 molecule-1
implying that at the onset, the tetrasubstituted porphyrin molecules are not aggregated
or stacked.91 However, this arrangement is not stable to pressure, and as the film is
compressed, the molecules are forced to rearrange.
Figure 3.5: Isotherms of PdP4, pure and mixed with ODPA (PdP4:ODPA), on a water
subphase.
The change in the aggregation of PdP4 during compression can be observed
with reflectance UV-vis spectroscopy of the Langmuir monolayer (Figure 3.6). As the
film is compressed from a MMA of 370 2 molecule-1 through 220 A2 molecule-1, the
A,max remains between 416 and 417 nm, similar to the 7,max observed for the non-
aggregated porphyrin in EtOH. At areas between 220 and 100 A2 molecule-1, the Soret
Band shifts to 418 419 nm, and below 100 2 molecule-1 the Soret Band shifts
further to near 421 nm. The shift in the Soret Band suggests a change in the


15
Porphyrin containing films often have oblique dichroic ratios of approximately
1.5, corresponding to the chromophores lying parallel to the substrate. For example,
Zhang et al., obtained such a result in LB films containing a free base tetraphenyl
porphyrin either pure or mixed with stearic acid, where the porphyrin was the
hydrophilic head group with long alkyl substituents.33
1.1.2. Self-Assembled Films
Zisman introduced SAMs to the literature little more than 50 years ago. His
studies involved self-assembling long-chained alcohols onto a glass surface using
hexadecane as the inert solvent.18 This study showed that films prepared in this
manner had wetting properties similar to those seen in films prepared by the LB
technique.
Sagiv et al. studied octadecyltrichlorosilane (OTS) on hydroxylated surfaces,
such as glass, to form a siloxane polymer. Multilayers were produced if the
amphiphile was terminated at both a and co positions by surface-active groups.15-34
When a and to positions were two different functionalities, subsequent dipping in self-
assembly solutions produced non-centrosymmetric films. Unfortunately, studies have
shown that small defects in the early layers can magnify upon multilayer formation
such that nearly all order breaks down by the tenth layer.20 The SA of OTS is now
commonly used for hydrophobisizing glass slides for LB substrates.
The chemisorption of thiols on gold was initiated by Nuzzo and Aliara35 and
continued by Porter,36 Whitesides,37 and others. Alkyl thiols, in which the chain
lengths range from one carbon to over twenty, have been studied. Closely packed
layers were observed when the chain length exceeded eleven carbons.36 The gold
surface used in these studies was formed by vacuum evaporation onto cleaved alkali-


106
As an additional confirmation of the successful tethering of MnP4 to the
zirconated ODPA template, XPS was performed. A clear peak was observed for Fls,
N)sand Mn2p3 electrons. The Zr3d3 and Zr3d5 and P2p3 were also observed. From the
XPS it is apparent that the MnP4 has been incorporated into the film and that the film
is stable to UHV.
Figure 4.18: XPS of MnP4 SA film. The insert is an enlarged view of the same
spectrum between 200 and 80 eV.
4.4 Conclusions
MnP4 molecules can be successfully incorporated into ultrathin films using both
the LB and SA techniques. From the UV-vis perspective, these films appear very
similar. In each film, there is a characteristic Soret Band. Typically, this band occurs


165
(19) Bartell, L. S., Ruch, R.J. J. Phys. Chem 1956, 60.
(20) Ulman, A. An Introduction to Ultrathin Organic Films: From Langmuir-
Blodgett to Self-Assembly, Academic Press: Boston, 1991.
(21) Zasadzinski, J. A.; Viswanathan, R.; Madsen, L.; Gamaes, J.; Schwartz, D. K.
Science 1994,263,1726-1733.
(22) Gaines, G. J. Insoluble Monolayers at Liquid-Gas Interfaces', Wiley-
Interscience: New York, 1966.
(23) Tredgold, T. H. J. Mater. Chem. 1995, 5, 1095-1106.
(24) Aston, M. S. Chem. Soc. Rev. 1993, 67-71.
(25) Orrit, M.; Mobius, D.; Lehmann, U.; Meyer, H. J. Chem. Phys. 1986, 85, 4966-
4979.
(26) Mobius, D.; Orrit, M.; H., G.; Meyer, H. Thin Solid Films 1985,132, 41-53.
(27) Drago, R. S. Physical Methods for Chemists', Saunders College Publishing:
Orlando, 1992.
(28) Byrd, H.; Pike, J. K.; Talham, D. R. Chem. Mater. 1993, 5, 709-715.
(29) Byrd, H.; Whipps, S.; Pike, J. K.; Talham, D. R. Thin Solid Films 1994, 244,
768-771.
(30) Offord, D. A.; Sachs, S. B.; Ennis, M. S.; A.Eberspacher, T.; Griffin, J. H.;
Chidsey, C. E. D.; Coliman, J. P. J. Am. Chem. Soc. 1998,120, 4478-4487.
(31) Practical Surface Analysis', 2nd ed.; Briggs, D.; Seah, M. P., Eds.; John Wiley
and Sons: Chichester, 1990; Vol. 2.
(32) Seah, M. P.; Dench, W. A. Surface Interface Analysis 1979,1, 1-11.
(33) Zhang, Z.; Nakashima, K.; Lai Verma, A.; Yoneyama, M.; Iriyama, K.; Ozaki,
Y. Langmuir 1998,14, 1177-1182.
(34) Sagiv, J. J. Am. Chem. Soc. 1980,102, 92.
(35) Nuzzo, R. G., Aliara, D.L. J. Am. Chem. Soc. 1983,105, 4481.
(36) Porter, M. D.; Bright, T. B.; Aliara, D. L.; Chidsey, C. E. D. J. Am. Chem. Soc.
1987,109, 3559-3568.
(37) Strong, L., Whitesides, G.M. Langmuir 1988, 4, 316.
(38) Byrd, H.; Whipps, S.; Pike, J. K.; Ma, J.; Nagler, S. E.; Talham, D. R. J. Am.
Chem. Soc. 1994,116, 295-301.


3
of the mechanics of both the LB and SA processes is important in appreciating thin
film research and its application to many areas of science.20
1.1.1 Langmuir-Blodgett Films and Characterization
1.1.1.1 Langmuir monolayer formation: the isotherm. The Langmuir
monolayer is achieved by placing droplets of an amphiphile solution, in a volatile
solvent such as CHC13, on the aqueous subphase in such a way as to uniformly spread
the compound on the surface. Typically, the presence of an amphiphile works to
decrease the surface tension, and the difference is defined as the surface pressure. In
Equation 1.1, II is the two-dimensional surface pressure typically measured in mN m'1,
Yo is the initial surface tension of the subphase and Yf is the surface tension of the
subphase and film.22>23
n =y0-rf 0-i)
The record of the monolayer formation on the water surface, the II vs. area (A)
isotherm, depends on the change in the surface pressure with a change in the mean
area per molecule (MMA) on the surface.15-22 The surface pressure is measured using
a sensitive microbalance, such as a Wilhelmy balance, while the area is computer
controlled using movable barriers, which define the monolayer boundaries.
Upon room temperature spreading, the monolayer is at a very low density and
behaves like a two-dimensional gaseous phase (Figure 1.1). In this phase, the
molecules are theoretically not in constant contact with one another, although
aggregation may occur depending on the affinity of the amphiphilic molecules for one
another. There are random collisions, but there is no appreciable increase in surface


128
Figure 5.12: MnP4 substituted film rinsed in chloride and t-butylamine solutions.
To further promote chloride binding, the chloride-containing EtOH/H20
solutions were heated. Heating the solution worked remarkably well at incorporating
chloride binding, and the low energy peak developed significantly. After being left
overnight, the red peak was much more persistent. This result may indicate that in the


72
Figure 3.11: Transmission UV-vis of PdP4 films transferred at high and low MMA.
Absorbance scale corresponds to the film transferred at 300 2 molecule'1. The
absorbance for the film transferred at 130 2 molecule'1 has been divided by 10.
As the pH was raised, the amphiphiles became slightly more water-soluble and
the monolayer was increasingly susceptible to creep. However, films of PdP4
compressed to 300 2 molecule"1 were deposited onto zirconated ODPA templates
from subphases of pH 9.4 and 11.1. As the pH increased, A.max of the Soret Band of
the transferred film decreased to 414 nm for the film deposited at pH 11.1. This was
the lowest value of X.max, and therefore, the least aggregated LB transferred film of
PdP4. The X,max of this Soret Band corresponds to that of chromophore PdP4 in EtOH
at 10"12 M which is believed to be non-aggregated.
Consistently, D = 1 0.02 when measured at 0 incidence, indicating no
preferred in-plane orientation of the chromophore in the PdP4 and PdPl films.
However, in all films, D 1 when measured at 450 incidence. For films transferred at
high surface area, it is expected that the porphyrins should lie flat with all four
phosphonates tethered to the surface. Indeed, this is observed for films transferred at


76
Figure 3.13: Transmission UV-vis of films of PdPl transferred at high and low
MMA.
X-ray diffraction from alternating films of PdPl transferred at 52 2
molecule'1 onto a zirconated ODPA template gives a layer thickness of 61 (Table
3.2). This thickness is larger than that of the alternating films of ODPA/Zr/PdP4 or
ODPA/Zr/ODPA bilayers.28 Since optical spectroscopy indicates the molecules lie
flat, the enhanced thickness of the layer suggests they transfer as stacked bilayers or
multilayers. Further evidence for this arrangement comes from the film stability
studies, described below, which indicate that part of the transferred film of porphyrin
PdPl is physisorbed to the surface.


129
presence of a large excess of chloride ions, chloride binding is much less mobile and
more difficult to displace (Figure 5.12).
Rinsing in /-BuNH2 in room temperature EtOH caused the complete and
immediate displacement of the chloride ligands. It is known that imidazoles tend to
bind more efficiently to the porphyrins than chlorides, and so it is possible that the
band at 462 nm represents imidazole binding.111
5.3.2.4. Preparing the substituted film from a chloride containing solution. To
avoid phosphonic acid binding upon film formation, a layer of MnP4 was assembled
from a 0.1 M solution of chloride onto an ImODPA layer (Figure 5.13). Initially, the
chloride binding was not obvious, and the Soret was slightly blue shifted relative to
phosphonic acid binding.
0.020
SA MnP4
350 400 450 500 550 600
Wavelength (nm)
Figure 5.13: MnP4 substituted from a 0.1 M Cl' solution onto an ImODPA layer, and
compared to a MnPO solution with ImH binding.


113
persistent in the films is less important than that the imidazole is present and available
to bind.
5.2 Solution Studies
Ligand effects as well as chromophore orientation and aggregation are
primarily reflected in the shape or shift of the Soret Band or Band V. Therefore, the
behavior of this band was carefully monitored. In addition, the ratio of Bands V to VI
could be observed resulting from a change in the ligand environment.115 Observed
changes in the Soret Band in a non-coordinating solvent solution of a potential ligand
are partially due to polarizability of the ligand. High polarizability of the axial ligand
will lead to less negative charge induced on the porphyrin through the metal, and the
Soret will shift to lower energies.115
As mentioned in Chapter 4, the MnP4 spectrum demonstrates a strong
tendency to intramolecularly bind to the phosphonic acid head-groups on the alkyl
chain substituents. Because the imidazole binding is crucial in the catalysis studies, it
was important to consider the ability of imidazole to replace phosphonic acid ligands
in these systems. According to Arasasingham, the displacement of a water or hydroxy
ion by imidazole is favored,114 however, the ability of imidazole to replace
phosphonate ligands had no literature precedence.
5.2.1 MnPO and MnP4 with ImH
To determine the electronic effects of binding the imidazole in the absence of
potential phosphonate ligands, an imidazole containing no long phosphonic acid chain
(ImH) was added to a solution of MnPO, where the concentration of the MnTPP was
held constant and the ratio of ImH:MnTPP was increased. With MnPO, as an excess


154
films (Figure 6.5). The lower yield could be due to the aggregated nature of the
chromophores reducing the active porphryin surface area.
Table 6.2: Conversion of cyclooctene to cyclooctene oxide with 40 pmol cyclooctene
and 5 pmol PhIO in lmL of solution using MnP4 LB film in 24 hr.
LB MnP4
Cyclooctene oxide
Yield
Turnovers
Bleaching
Blank
4.0%
Homogeneous
11.0%
550
<50%
Film
15.0%
750
<20%*
* The amount of bleaching was difficult to determine due to the broadened Soret
Band observed prior to the catalysis reaction.
6.2.1,3. Oxidation yield dependence on reactant ratios. Changing the ratio of
substrate to oxidant was also investigated. Whereas the prior studies focused on a
ratio of 40:5, 60:5 and 20:5 substrate to oxidant ratios were also examined over 24 hr.
Changing the substrate to oxidant ratio resulted in yields similar to that seen for the
40:5 experiment. In the 60:5 case, the overall yield was, again, around 20%; however,
the porphyrin film experienced slightly less bleaching than observed previously with
less substrate. The 20:5 case behaved similarly to the 60:5 and 40:5 experiments, and
the yields were approximately the same (Table 6.3).


31
When the chromophores are interacting with the transition dipole moments
parallel, the exciton energy can be described by Equation 1.9:
V =
(1.9)
where M is the transition dipole moment, R is the center-to-center distance, N is the
number of chromophores, and a is the angle between R and M (Figure 1.16). So, if a
< 54.7, V will be positive, and the exciton splitting will be greater and a red shift will
be observed as the transition shifts to lower energy. A red shift is observed in what are
called J-aggregates where both Mx and My make angles less than 54.7 with the R
vector. If a > 54.7, V will be negative, and the exciton splitting energy will be lower
leading to a blue shift in the spectrum. When Mx and My are both greater than 54.7
from R, the aggregates are termed H-type. If ax < 54.70 and ay > 54.7 , the spectral
components will split and part of the band will shift red and part will shift blue; this
spectral behavior is seen in edge-to-edge type aggregates. There can be combinations
and varying degrees of these types of interactions within an aggregated domain
possibly leading to complicated spectra, but in general, the optical spectra ease
identification of electronic behavior of porphyrin chromophores (Figure 1.16). 76,83,84


of the emitted electrons can be related to the excess energy and to the strength of the
electrons binding by Equation 1.3, which is the Einstein photoelectric law:27
11
Eki=hv-e^)-Eb
(1.3)
where Eb is the binding energy, e is the charge of the electron, h is Plancks constant, v
is the frequency of the radiation, and 4> is the work function corresponding to the
minimum energy required for ejection of an electron.
Detector
Ekin hv -
Monochromatic X-ray
Ream
Figure 1.5: Schematic of XPS experiment.
The XPS spectrum plots electron counts versus binding energy. Binding
energies are unique to each element present in the film, as well as to that elements
chemical environment and oxidation state. Therefore, from a scan over a wide range
of binding energies, called a survey scan, XPS results can be used to define the
elements present in the sample. A more extensive scan, or a multiplex scan, over a
narrow range of binding energies can clarify peak splitting, which can be assigned to a
change in the chemical environment or oxidation state. Offord, et. al., in their study of
a Ru-porphyrin linked to a thiol on gold SA film containing a percentage of imidazole
terminated thiol surfactants, observed two peaks within the Nls region of the XPS


55
Approximately 5 mL of the above oxidant/substrate solution was transferred
into a small Erlenmeyer flask and from there loaded into the flow cells used for
studying catalysis with the films. Also, blanks and homogeneous solutions were
loaded into cells containing blank films (no catalyst) for studying product yields
affected by the flow cell.
Viton cell:
Bottom plate
Groove with
Viton o-ring
Viton cell:
Top plate
Figure 2.4: Schematic of catalysis cell, top view.
The flow cells were built by the University of Florida machine shop. The cell
was made from two blocks of Delrin into which was carved a cell with dimensions:
0.96 x 1.38 x 0.039. Inlet and outlet tubes were place at the cell edges. One end
of a 1 length of 1/16 ID Viton tubing (Cole-Parmer, Vernon Hills, IL) was
connected to the inlet port and the other end was submerged in the reaction solution.
A Cole-Parmer Masterflex peristaltic pump (model 7553-70) (6-600 rpm) with an
easy-load head was used to introduce the solution into the cell, then the open end of
the Viton tubing was removed from the solution and connected to the outlet port of the
cell. The solution was circulated around the film using the peristaltic pump.


123
Figure 5.8: UV-vis of an ImODPA/ MnP4 film after drying.
5.3.1.3. MnPO linked to ImODPA containing LB films. MnPO, a porphyrin
with no alkylphosphonic acid chains, was assembled into ImODPA SA films to study
the imidazole binding in a simplified system. The only available methods of
absorbing MnPO to these films were through the imidazole or through aggregation of
chromophores, i.e. physisorption, to already chemisorbed porphyrins. Upon rinsing,
any physisorbed MnPOs should be washed away. Figure 5.9 shows the UV-vis of a
layer of MnPO attached to a 25% ImODPA/HDPA LB film. The absorbance intensity
of the MnPO film was much less than films containing the MnP4, but the porphyrin
was clearly present indicating the imidazole binding was active. After 60 min in a hot
CHC13 solution, the absorbance intensity of the film did decrease indicating
chromophore loss. However, the imidazole binding was somewhat stable to hot
CHC13 as the chromophores were not completely removed after 60 min in the solvent.


10
elucidation of information about films containing new amphiphiles. For example, by
comparing the areas of the alkyl stretches of a new amphiphile to that of well-
understood fatty-acid films, an idea of the transfer quality can be obtained. This tool
is particularly helpful in studying monolayers with transfer ratios varying from unity.
ATR-FTIR can also indicate the packing nature of the alkyl chains. If the
chains are in a mostly tram configuration and close-packed, the asymmetric CH2
stretch (vaCH2) will occur at 2918 cm'1 and have a full width at its half maximum
(FWHM) of ca. 20 cm'1. The symmetric CH2 stretch (vsCH2) will occur at ca. 2852
cm'1. If there are a significant number of gauche interactions in the chains, the vaCH2
and vsCH2 stretches will shift to higher energies (ca. 2924 cm'1 for the vaCH2 and ca.
2856 cm*1 for the vaCH2 stretches).2829
(XO000000600
Figure 1.4: Schematic of the ATR-IR Experiment.
XPS is a method used to determine the elemental make-up, and possibly,
atomic proportions within a film based on the photoelectron effect. XPS measures the
energy of an expelled electron as the surface is bombarded with a monochromatic X-
radiation source (Figure 1.5). When a high-energy source is applied, the kinetic energy


108
Unfortunately, though the Soret Band at All nm is usually associated with
chloride binding, Soret Bands around 460 nm can be associated with a number of axial
ligands and chromophore interactions making difficult absolute characterization of the
porphyrins ligand and aggregation environment. However, ultimately, the ligand
filling the axial position on the chromophore is less important than its lability. If the
metal center of the porphyrin is available for oxidation, the catalyst will be active.
Also, as will be discussed in Chapter 5, if the imidazole can displace the axially bound
ligand, it can positively influence the catalysis.


62
and PdPl absorb at 411 nm at 10*11 M, so the long chains have no effect on the Soret
Band of the non-aggregated chromophore.
Figure 3.3: Solution UV-vis of Pd-porphyrins in CHC13: A) PdP4, B) PdPl. The
absorbance scale refers to the 1CT6 M curve. The 10'" M curve has been enlarged for
Band comparison.
The studies of the same molecules at identical concentrations in EtOH and
water showed very different behavior (Figure 3.4). In EtOH at 10'11 M, both PdP4 and
PdPl show Soret Bands at 414 415 nm. This peak is significantly to the red of the
Soret Bands in CHCI3; however, it is known that more polar solvents tend to stabilize


68
Figure 3.9: Reflectance UV-vis of 10% PdP4: 90% ODPA on a water subphase.
The molecular areas in Figures 3.5 and 3.7 are weighted averages of the
porphyrin and ODPA molecules. The MMA of the porphyrin molecules in the mixed
films can be calculated using Equation 3.1: 89
^Mix
(S/VR + NSqta )
(N+1)
(3.1)
where Sm¡x is the MMA of the mixture determined from the isotherm, Spor is the
MMA of the porphyrin within the mixed films, Sodpa is the MMA of the ODPA
amphiphile in pure ODPA films, and N is the molar ratio of ODPA to porphyrin.
Spor was calculated in the ODPA mixtures of each porphyrin at pressures of 5 mN nr1
and 15 mN nr1 and the results are plotted in Figure 3.10.


7
a mirror on the base of the trough and reflecting a beam through the monolayer onto
this mirror, and back into a detector. These studies can help determine the onset of
aggregation in films with such a tendency.25-26
Ll.1.3 Langmuir-Blodgett film formation. LB films are formed by vertically
transferring Langmuir monolayers from the water surface onto a solid support. There
are three common vertical dipping techniques, which form X, Y, and Z-type films
(Figure 1.2). 15>23 In X-type LB films, a Langmuir monolayer is transferred onto a
hydrophobic substrate in such a way as to maintain head to tail type interactions. In Z-
type LB films, the monolayer is transferred onto a hydrophilic substrate also forming
head to tail interactions. X- and Z-type films can be prepared on a specially designed
trough, which allows one stroke to be made through a monolayer and the next to be
made through a clean subphase. However, some amphiphiles have a preference for
this type of interaction and upon regular dipping, these structures form spontaneously.
Y-type multilayers are most common and can be prepared on either hydrophilic or
hydrophobic substrates. Y-type multilayers are typically the most stable due to the
strength of the head-head, tail-tail interactions.15
X-type
Z-type
Y-type
Figure 1.2: Schematic of X-, Y-, and Z-type Langmuir-Blodgett multilayers.


5.18 XPS multiplex scan of N1 s region of ImODPA/MnP4 film self-assembled
out of 70/30 CH2CI2 solution. The dashed lines represent the Gaussian
peak fits 136
5.19 XPS multiplex scan of ImODPA/MnP4 film self-assembled from a 70/30
mixture in EtOH/FLO 136
5.20 ATR-IR of ImODPA SA film 138
5.21 Increase in absorbance intensity of 2918 cm'1 peak in ImODPA with
SA time 139
5.22 ATR-IR of alkyl region of: A) MnP4 substituted on a 100% ImODPA base
capping layer, B) MnP4 substituted on a 25% ImODPA base
capping layer 141
6.1 SA MnP4 film before and after 24 hr. catalysis run with 40:5:20
cyclooctene: PhIO:decane in CH2CI2 148
6.2 SA MnP4 film before and after 2 hr. catalysis run with 40:5:20
cyclooctene: PhIO:decane in CH2CI2 149
6.3 UV-vis of MnP4 film SA from chloride containing solution used in
catalysis with PhIO after 6 hr 150
6.4 Bleaching of MnPO in homogeneous catalysis reaction with PhIO 152
6.5 MnP4 LB film before and after 24 hr catalysis reaction 153
6.6 S A ImODPA/SA MnP4 studied with PhIO for epoxidation of cyclooctene 156
6.7 SA ImODPA/SA MnP4 studied in the epoxidation of cyclooctene
using H2O2 159
6.8 SA ImODPA/SA MnP4 after rinsing and after 24 hr in catalysis reaction
with excess H2O2 161
6.9 SA ImODPA/SA MnP4 film with catalysis using 8 pmol cyclooctene
to 0.2 pmol H2O2 162
xii


19
above divalent series is Cu(II).48>57 The Cu atoms in these phosphonate materials are
five coordinate and form a distorted tetragonal pyramidal geometry.
Mallouk has prepared a series of lanthanide phosphonates. The structure of
these materials is given as Ln(III)H(03PR)2, where Ln represents La, Sm, or Ce. The
lanthanide-series phosphonates are more soluble than the zirconium solids, but less
soluble than the divalent materials. Therefore, single crystal data was not easily
obtained.5859
ATR-IR provides a facile method for characterization of the metal phosphonate
lattice formation. Vibrational modes assigned to the phosphonate are extremely
sensitive to the mode of metal binding. Thomas et al. have assigned the va(CH2)
vibrational frequencies for the divalent metal-phosphonates to be in the range of ca.
1050 1100 cm"1 where the vs(CH2) stretches occur ca. 970 990 cm'1.60 Each metal
phosphonate material has characteristic stretches in these regions.
1.2.2. Self-Assembled Films Incorporating Metal Phosphonate Binding
After Sagiv's work with self-assembling films of octadecyltrichlorosilane
(OTS), it seemed a natural step to translate the formation of the thermodynamically
stable and insoluble layered metal phosphonate solids into ultrathin films. Self-
assembly was the first technique employed to produce metal phosphonate thin films.
Mallouk and coworkers formed the metal phosphonate self-assembled films by first,
exposing a silicon or gold surface to an appropriate template forming alkyl-mercaptan
that was substituted with a terminal phosphonic acid.61-62 This phosphonic acid was
active toward the metal salt solution in which the substrate was then dipped. After
metallating the surface, the substrate was dipped in a solution of an a, co-
bisphosphonic acid, which left another phosphonic acid on the surface to be


89
The obvious difference between MnPO and MnP4 is the presence of the four
C,8-chain phosphonic acid tethers linked to the phenyl rings of the MnP4. Therefore,
the peak at 464 nm is, as previously mentioned, probably due to intramolecular
phosphonate binding. However, the structures of the two chromophores also differ in
that MnPO has four pentafluoro-phenyl substituents, and MnP4 has an ether linkage to
the alkyl chain at the para-position of the phenyl groups. For a more direct
comparison, a compound incorporating similar p-methoxy-tetrafluoro-phenyl
substituents was prepared (MnP-4MeO). This compounds spectral behavior was
identical to the MnPO compound, further indicating that phosphonate binding causes
the Soret peak at 464 nm.
OCH-5
4.2.1.3. MnPO in solution with ethvlphosphonic acid. Though the alkyl chains
may have altered the chromophore interaction in solution,134 the stronger UV-vis
effects were likely due to the presence of the intramolecular R-PO(OH)2 ligands. The
binding of the phosphonic acids to the central porphyrin metal was confirmed by


50
throughout the deposition. A variety of surface pressures were used for transfer and
will be described in more detail in Chapter 4.
To prepare SA Mn-porphyrin films, 1 mL of a 0.5 mg mL'1 MnP4 solution in
EtOH was diluted to 30 mL with a 9/1 EtOH/H20 mixture in a 50 mL vial.
Alternatively, a 0.5 mg mL'1 MnP4 solution in CHC13 was diluted with pure CHC13 or
CH2C12. The zirconated ODPA surface was exposed to the SA solution for 2 hr unless
otherwise specified. After 2 hr, there were typically some physisorbed chromophores,
which were rinsed off the surface using a hot solvent such as CHC13 or CH3CN.
As is discussed in Chapter 4, halogenated solvents were originally chosen as
self-assembly solvents to eliminate possible ethoxide or water binding. However, the
oxide coating on the exposed zirconated ODPA template is soluble in EtOH/H20
solvents making the zirconium available for binding the phosphonic acids of the
porphyrin capping layer. From UV-vis studies, the films formed from these different
solvent systems appeared to behave similarly. Therefore, because the film formation
mechanism from EtOH/H20 was better understood, this solvent mixture was normally
used.
To induce chloride binding at the Mn-porphyrins axial position, a SA solution
containing approximately 0.01-0.1 M t-BuNH3+ Cl' along with the porphyrin in
EtOH/H20 was prepared. The zirconated ODPA template was submerged in this
solution for 2 hr. Alternatively, chloride ions were incorporated into the aqueous
subphase used for LB transfer of the MnP4 monolayers using NaCl at 0.1 M and
greater concentrations.
From UV-vis results of the MnP4 and MnPO with ethylphosphonic acid, it
appeared that the phosphonic acid might cause the Mn(III)-porphyrin to go through a
spin state crossover from high-spin to low-spin Mn(III). In order to examine this
magnetic change, the Evans NMR method was used.119120 A solution of 10% t-


94
scenario. In the first region of the isotherm ('a' of Figure 4.7), the chromophores and
the phosphonic acids remained on the water surface and were simply compressed.
Figure 4.7: Isotherm of MnP4 on water subphase.
During the plateau region of the isotherm ('b' of Figure 4.7), the chromophores were
pushed off the water surface and the porphyrin rings started overlapping. There were
likely some dimers forming and not all phosphonic acid end groups reached the
surface. In region c of Figure 4.7, the MMA was approximately 100 2 molecule'1,
implying the presence of dimers, which were then further compressed until the
monolayer collapsed. At this point, the film was likely not a true monolayer as the
chromophores essentially formed a bilayer.
The separation of the chromophores from the water surface was accompanied
by overlapping, which was also indicated by a consequent shift in the 7.max detected by
reflectance UV-vis (Figure 4.8). In region 'a', the Xmax was at 457 nm. While in


interaction in the films. Because chromophore aggregation was expected to inhibit
catalysis, film preparation conditions were sought in order to avoid this.
LB and SA films of pure manganese porphyrins were successfully prepared by
a number of different methods. Aggregation appeared insignificant when transferred
at high mean molecular areas and when the films were self-assembled. The pure
manganese porphyrin films were successful at catalyzing the epoxidation of
cyclooctene using iodosylbenzene as the oxidant.
To activate the porphyrin for catalysis with peroxide oxidants, a heterocyclic
ligand was also incorporated into the manganese porphyrin containing films. The
heterocyclic ligand used was an imidazole substituted with an octadecylphosphonic
acid chain. Both the manganese porphyrin and the imidazole amphiphile were
tethered to a zirconium phosphonate network, first for ease of film synthesis and
second, to stabilize the film for use in the catalysis reactions.
Though significant catalyst degradation has been reported in homogeneous and
alternative heterogeneous catalysis studies, the manganese porphyrin and imidazole
containing zirconium phosphonate films were generally more resistant to degradation
under catalysis conditions. The stability of the films toward epoxidation conditions
has led to easily recyclable catalysts.
xiv


134
5.3.5. Characterization of films containing MnP4 and ImODPA by XPS and ATR-IR
5.3.5.1. XPS results of pure MnP4 and pure ImODPA films. Though the UV-
vis is the most well documented method of characterization for porphyrin films, the
ImODPA had no clear transition in the UV-vis. Therefore, to characterize the
ImODPA self-assembled film prior to the MnP4 substitution, ATR-IR and XPS were
employed. To study the formation of the ImODPA films by XPS, a layer of ImODPA
was self-assembled onto a zirconated ODPA template on a silicon wafer.
Figure 5.17: XPS multiplex scan over the Nls region of A) ImODPA, and B) MnP4
self-assembled films. The dashed line represents the Gaussian peak fit.


CHAPTER 5
INCORPORATION OF AN IMIDAZOLE LIGAND INTO MANGANESE
PORPHYRIN CONTAINING ZIRCONIUM PHOSPHONATE THIN FILMS
5.1 Background
As in Chapter 4, the chromophore catalyst studied was a tetraphenyl porphyrin
para-substituted with four octadecylphosphonic acid groups (MnP4), which could
tether the porphyrin directly to the zirconium surface. For comparison, the model
porphyrin MnPO with no phosphonic acid chains was also examined. The heterocyclic
ligand used for these experiments was an alkylphosphonic acid imidazole (ImODPA),
which could also be easily attached to the zirconium surface. From the propensity of
the imidazole to protonate in the presence of HBr during the ImODPA synthesis, the
imidazole unit was the bromide salt upon film preparation (Figure 5.1). Deprotonation
of the imidazole was attempted in order to facilitate its binding to the metallo-
porphyrin. To study the porphyrins UV-vis sensitivity to an imidazole ligand in
solution, an imidazole with no alkyl chains (ImH) was also used for solution studies.
The anticipated structures of the mixed MnP4/ImODPA and MnPO/ImODPA
films are shown in simplified form in Figure 5.2. The chromophore is at the exterior
of the film and available to catalyze the reaction of interest. The bulky chromophore
leaves vacant sites available for the ImODPA, which is tethered to the zirconium-
phosphonate network under and around the chromophore (Figure 5.2). Multiple
109


18
alkyl phosphonates, it was found that there is a tilt angle in the chains of between 55
and 60. This tilt allows for maximization of the van der Waals forces between the
chains even within the solid-state materials. Though the structures formed are dictated
by the geometry of the inorganic lattice, the hydrophobic region does rearrange to
balance these strong forces with the maximization of their overlap.53 A change in the
organic group can lead to very different structures and properties of the solids. Bulkier
groups may form new crystal structures or have three-dimensional metal lattice
formation. Also, the different organic groups can impart different function to the
films.
1.2.1.2. Divalent and trivalent metal phosnhonate solids. After extensive
research on the zirconium phosphonate solids, interest branched to divalent and
trivalent metal phosphonates. The poor solubility of the zirconium phosphonate solids
in most standard solvents meant achieving single crystals was difficult; therefore, most
of the crystal structure data was achieved from powder X-ray diffraction patterns.
However, di- and trivalent metals tend to be soluble in acidic solutions, allowing
single crystals to be obtained by slowly changing the solvent pH or the metal ion
concentration.
Metal phosphonate materials have been prepared with a variety of different
divalent metals such as Mg2+, Mn2+, Zn2+, Ca2+, and Cd2+.54-56 From the crystal
structures, it was determined that the composition of the divalent series metal
phosphonates is Mn(03PR)H20 for Mg, Mn, Zn, Ca and Cd. In these materials,
layers of the metal atoms are octahedrally coordinated by five phosphonate oxygens
and one water molecule, with each phosphonate group coordinating four metal atoms
making a cross-linked M-0 network. A second structure, the orthorhombic
Mn(H03PR)2, was observed for the Ca phosphonates. A structural exception to the


115
(Figure 5.3B). This peak was in reasonable alignment with the peak observed in the
MnPO solutions under the same conditions. Imidazole ligands are not reported to
encourage aggregation effects; therefore, these results again imply that the blue shift
represents imidazole binding. This blue shift corresponds to a similar shift reported by
Bruice et. al in their solution studies of a Mn-porphyrin with an increasing
concentration of an imidazole ligand.111
At the high concentrations of ImH relative to porphyrin, the imidazole filled
either one or both of the axial positions on the metallo-porphyrin. The imidazole,
therefore, successfully displaced the phosphonic acid. Also, in the solutions
containing excess ImH, Band Va, which was assigned to free-base porphyrin, is
reduced. With the competition between imidazole and phosphonic acid for the axial
position, the phosphonic acid is obviously less likely to demetallate the Mn-porphyrin.
At lower imidazole concentrations, the blue shift was less obvious. However, the
effective concentration of phosphonic acids on the MnP4 in the vicinity of the metal
was very high, so the solution concentration of ImH had to be large to compensate.
5.2.2. MnP4 and MnPO with ImODPA
When ImODPA was added to MnPO in CHC13, the blue shift indicating
imidazole or phosphonic acid binding was not observed. Instead, the Soret Band
shifted from 477 nm to 483 nm. This red shift in the Soret Band is due to bromide
displacing chloride as the axial ligand. Bromide originates from the ImODPA, which
is originally a protonated amine-bromide salt. Mn-porphyrins with bromide ligands
absorb at higher wavelengths than with chloride ligands because bromide is less
electronegative and more polarizable than chloride shifting the Soret Band to lower
energies.115 A close look at the region ca. 418 nm shows that Band Va is also
appearing. This band has been attributed to the presence of free-base porphyrins,


Ill


ImODPA
Figure 5.2: Schematic of MnP4 and ImODPA films.
A variety of methods were employed in order to accommodate the porphyrins
large MMA and encourage its binding to the imidazole in the films. These formation
procedures, which were motivated by a number of intentions, will be described in this
chapter. First, the Mn-porphyrin/imidazole binding is in an equilibrium state. In order
to encourage the imidazole binding, or at least its availability for binding, the
imidazole had to be present in excess relative to the porphyrin. To insure excess
imidazole, this layer was often prepared first by either the SA or LB method. The
hydrophilicity of both the phosphonic acid and the imidazole chain terminating groups


21
The zirconium metals have such a high oxophilicity for the phosphonate
oxygens, that when a phosphonic acid amphiphile is spread on the surface of a
zirconium cation containing aqueous subphase, the monolayer crystallizes before it
can be transferred. Therefore, a three-step deposition procedure has been developed.
A phosphonic acid containing monolayer is formed on the surface of a pure water
subphase and transferred onto a hydrophobic substrate. Onto this phosphonic acid
surface, a layer of zirconium is assembled, followed by the transfer of a second LB
monolayer containing a phosphonic acid. This three-step deposition technique will be
described in detail in Chapter 2.28>38
Advantages of this three-step technique include the fact that at the hydrophilic
stage, the monolayer is stable and can be independently characterized by ATR-FTIR
or XPS, etc. Second, this method allows the formation of alternating films in which
the template and capping layers do not have to be formed of the same amphiphile. The
option of forming alternating films is important because some amphiphiles do not
transfer on the down stroke but will transfer onto an ODPA template layer. A
disadvantage of the three-step deposition of the phosphonate films occurs at the self-
assembly of the zirconium lattice. The self-assembly of the zirconium onto the ODPA
template causes the metal phosphonate lattice to be amorphous, whereas in a one-step
deposition, the metal lattice is crystalline.
An alternative technique of film formation is employed for the divalent and
trivalent metals.41 In these cases, the metal salts are dissolved in the aqueous
subphase, the phosphonic acid monolayer is formed on the surface, and the
hydrophobic substrate is dipped down and then up through the same compressed
monolayer forming a complete metal-phosphonate layer or an LB bilayer. The
crystallization of the metal-phosphonate lattice occurs on the slow upstroke of the film
through the monolayer (Figure 1.10).


150
Considering the original UV-vis spectra of the films indicated in the 2 hr and
24 hr experiments, there appeared to be a significant contribution from free-base
porphyrin in these films. From the studies described in Chapter 4 and 5, it was known
that self-assembling the MnP4 from a solution containing chloride ions helped
discourage the phosphonate from demetallating the porphyrin. To test if a decrease in
the film loading of free-base porphyrin affected the catalytic results, a film SA from a
chloride containing solution was employed for the 6 hr experiment. Again, some
bleaching of the porphyrin was observed, but it did appear that there was a significant
amount of the original chromophore present after catalysis. Also, there was no
significant contribution from free-base porphyrin to the UV-vis spectra even after the
catalysis run, so the catalysis does not cause the Mn-porphyrin to demetallate (Figure
6.3). However, the epoxide yield was not dramatically improved by eliminating the
free-base porphyrin from the films.
Figure 6.3: UV-vis of MnP4 film SA from chloride containing solution used in
catalysis with PhIO after 6 hr.


157
Table 6.4: Conversion of cyclooctene to cyclooctene oxide with 40 pmol cyclooctene
and 5 pmol PhIO in lmL of solution and in films containing imidazole.
SA ImODPA/SA
MnP4 Film
Cyclooctene oxide
Yield
Turnovers
Bleaching
Blank
1.5%-2.5%
Homogeneous
17.0%-20.0%
850-1000
Film
15.0%
750
<20%
6.2.1.5. Oxidation yield dependence on cell vs. vial used for reaction. The
above results appeared encouraging, with the epoxide yield consistently greater in the
immobilized catalyst reactions run in the flow cells over the homogeneous and blank
reactions run in the vials. When blank solution mixtures were run through the
catalysis cell with blank films, surprising results were obtained. After 6 hr, the blanks
in the vials ranged in product yield from 1.0% to 2.0%; however, in the flow-cells, the
epoxide yield was 6.0%-6.5%. The discrepancy between the yield in the blank cell
and in the vial was not related to a change in the overall concentration. However, the
difference was probably due to either the loss of internal standard into the flow-cell
material or the fact that the solution experiences more efficient stirring in the flow-cell
than in the vial.
Further, homogeneous reactions were also run in the flow-cell to examine if the
observed increased product yield with the catalytic films was due to the immobilized
catalyst or the act of performing the reaction in the cell. These results are shown in
Table 6.5. From a series of experiments, including GCs of a solution run after the


127
Figure 5.11: Reversibility of the chloride/phosphonic acid binding.
5.3.2,3. Rinsing the substituted MnP4 films in chloride ion solutions. Chloride
ions were deliberately added to the system by rinsing the films in a solution of tert-
butylammonium chloride (/-BuNH3+ C1). These results confirmed that the peak at 477
nm in the films represented the MnTPP(Cl). When the MnP4 substituted film was
rinsed in a room temperature EtOH solution of chloride ions, there was a clear Soret
peak splitting with the red peak occurring at 477 nm indicating that in excess, chloride
can bind at room temperature. When this film was then placed in a room temperature
chloride solution in 9/1 EtOH/H20 (the SA solvent mixture), Band Vii disappeared
and Band Vi intensified (Figure 5.12).


151
The behavior of the MnP4 films in the epoxidation reaction with PhIO over 6
hr showed up to a 20% reduction in the absorbance intensity of the peak at 464 nm.
The film could be recycled with ca. a 50% loss in catalytic activity, but catalysis could
still be observed.
For comparison, the bleaching of the porphyrin in the homogeneous solution
was studied (Figure 6.4). It appears that after 6 hr., there was as much as a 50%
bleaching of the active chromophores in solution. After 12 hr, the bleaching
observed was about the same as at 6 hr. The porphyrins immobilized in the zirconium
phosphonate films appear to be slightly more stable under most catalysis conditions.
Table 6.1: Time dependence of epoxidation of cyclooctene using 40 pmol
cyclooctene and 5 pmol PhIO in lmL of solution. To the homogeneous reaction was
added lnmol of MnPO.
Experiment
Cyclooctene oxide
Yield
Turnovers*
Porphyrin
Bleaching**
24 hr
Blank
Homogeneous
Films
4.98%
8.43%
35.1%, 20.8%
422
1755, 1040
<20%
6 hr
Blank
Homogeneous
1.0%-1.5%
6.0%-7.0%
300
< 50%
Films
30.3%, 29.0%
1515, 1450
<20%
2 hr
Blank
Homogeneous
Films
0.5%-1.0%
3.0%-3.4%
13.3%, 12.7%
150-170
665,635
None
* Turnovers calculated on number of oxidation cycles
** Bleaching determined from decrease in intensity of Soret Band in UV-vis


LIST OF FIGURES
Figure page
1.1 Schematic of an isotherm and corresponding monolayer behavior 5
1.2 Schematic of X-, Y-, and Z-type Langmuir-Blodgett multilayers 7
1.3 X-ray diffraction diagram 9
1.4 Illustration of ATR-IR Experiment 10
1.5 Schematic of XPS experiment 11
1.6 Schematic of polarized UV-vis experimental beam directions 13
1.7 Behavior of the oblique dichroic ratio versus an orientation parameter (P) 14
1.8 Crystal structure of zirconium phosphate 17
1.9 Comparison between tradition LB films and metal-phosphonate LB films 20
1.10 Schematic of formation of divalent or trivalent metal phosphonate films 22
1.11 Structures of porphyrin-type molecules A) porphine B) free base
porphyrin, and C) pthalocyanine 25
1.12 UV-vis spectrum of a metallo-porphyrin (PdTPP) 25
1.13 Outline of 16-member principle resonance structure of metallo-porphyrin 26
1.14 Goutermans four-orbital model 27
1.15 Transition dipole moments in metallo-porphyrin 30
1.16 Porphyrin chromophore interactions: The square represents the
chromophore and its disecting axes. A) H-type or face-to-face
aggregates; B) edge-to-edge aggregates; C) J-type or head-to-tail
aggregates 32
1.17 Suggested mechanism of olefin epoxidation catalyzed by MnTPP 35
Vlll


22
In the one-step method, the pH of the subphase is as crucial to successful
lattice formation as it is in the formation of the solids in aqueous solutions. If the pH
is too high, the affinity of the metals for the deprotonated phosphonates will be too
high and crystallization of the lattice will occur in the Langmuir monolayer rather than
upon transfer. As with the zirconium films, these films will be too rigid to be
successfully transferred.
Figure 1.10: Schematic of formation of divalent or trivalent metal phosphonate films.
If the pH is too low, the phosphonate will remain completely protonated, and the films
will transfer without metal binding. Fortunately, the pH effects on the crystallization
of the monolayer have signatures in the isotherm behavior.64 When the pH is too high,
the rigid monolayer gives an erroneous but characteristic isotherm that has a much


14
The dichroic ratio can be used to determine the chromophore orientation in a
film. In the case of films containing porphyrin chromophores, Orrit et al. determined
that the dichroic ratio can be translated into an orientation parameter (P) using the
graph shown in Figure 1.7,25 and hence, an orientation angle (0) can be established
using Equation 1.7:
P = (cos2 d)
(1.7)
0 represents the angel between the surface normal and the chromophores molecular
plane. As is often observed within the plane of a film containing porphyrins, if D is
unity, there is no preferred orientation. If D = 1.5, P = 0 and therefore, 0 = 900 as
measured from the surface normal.
Q
0.5
1.0
1.5
0.0 0.2 0.4 0.6 0.8 1.0
Orientation Parameter (P)
Figure 1.7: Behavior of the oblique dichroic ratio versus an orientation parameter
(P)-25


2.2.3Manganese Porphyrin/Imidazole Mixed Films 51
2.3 Catalysis 53
2.3.1 Catalysis using PhIO as an oxidant 53
2.3.2 Catalysis using Peroxides as oxidants 57
3 PALLADIUM PORPHYRIN CONTAINING ZIRCONIUM PHOSPHONATE
THIN FILMS 58
3.1 Background on Palladium Porphyrin Films 58
3.2 Results 61
3.2.1 UV-vis of Palladium Porphyrin Solutions 61
3.2.2 Langmuir Monolayers of Palldium Porphyrins 63
3.2.3 Langmuir-Blodgett Films 69
2.3.3 Conclusions 79
4 MANGANESE PORPHYRIN CONTAINING ZIRCONIUM
PHOSPHONATE THIN FILMS 83
4.1 Background 83
4.2 UV-vis Behavior of MnTPPs 85
4.2.1 Solution studies 85
4.2.2 Langmuir Monolayers 93
4.2.3 Langmuir-Blodgett Films of pure MnP4 95
4.2.4 Self-assembled films of MnP4 100
4.3 Conclusions 106
5INCORPORATION OF AN IMIDAZOLE LIGAND INTO MANGANESE
PORPHYRIN CONTAINING ZIRCONIUM PHOSPHONATE
THIN FILMS 109
5.1 Background 109
5.2 Solution Studies 113
5.2.1 MnPO and MnP4 with ImH 113
5.2.2 MnP4 and MnPO with ImODPA 115
5.3 Film Studies 117
5.3.1 Langmuir-Blodgett Films containing substituted MnP4 117
5.3.2 Mn-porphyrins substituted into self-assembled films of
ImODPA 124
5.3.3 Self-assembling the MnP4 and ImODPA from a
mixed solution 130
5.3.4 Other methods for preparing ImODPA and MnP4 containing
films 131
v


ACKNOWLEDGMENTS
First, I would like to thank some of the teachers who have pointed me toward
chemistry and supported me in this long educational adventure. I thank Mr. Roger
Craig from Lexington High School, for being so excited about chemistry, and Dr. Jim
McCargar, for being a tireless ambassador of general and physical chemistry, and for
encouraging (pushing?) me to pursue research opportunities outside of Baldwin-
Wallace College. I would also like to thank Dr. Gary Kosloski, who cared about my
music even after I defected to the other half of the liberal arts and sciences. And to
Dr. John West and Dr. William Samuels, I extend many thanks for accepting me into
their research programs and giving me two unique and valuable perspectives on
research outside of the academic environment.
I must thank Dr. Dan Talham for his patience, the limits of which, I have
surely tested. I would also like to thank him for accepting a physical polymer
chemistry convert and for teaching me to appreciate materials and surface chemistry.
I would also like to thank him for his time and effort in encouraging all of us to be
organized and effective speakers and writers. For that, I will be eternally grateful.
I could not have completed this document or the research that it describes
without the collaborative assistance from the Bujoli group in Nantes, France.
Especially to Fabrice Odobel, who has contributed significant time and energy to
11


142
of the different axial ligands, the evidence indicates that the aggregation is probably
not significant in these films.
Originally the spectral changes observed with rinsing were considered due to
some chromophore reorganization or possible solvent effects. However, the peak at
477 478 nm aligns with the porphyrins solvent UV-vis spectra only in the presence
of added chloride or bromide; therefore, halide binding has been concluded to cause
this red peak in the films as well. As mentioned, the chloride or bromide ligand
causing the Soret Band change is probably associated with the MnP4 as the original
axial ligand or bound to the imidazole through the HBr salt. When solubilized in hot
solvents, the halides then have the opportunity and the preference for binding at the
porphyrin metal center. The halide binding can be seen after rinsing in hot CHC13 or
hot CH3CN, as shown in Figures 4.11 and 4.14.
From ATR-IR, XPS, and UV-vis, the existence of ImODPA and MnP4 within
the films is confirmed. From the ATR-IR, the formation of the imidazole-containing
capping layer was determined. In addition, UV-vis and XPS confirms the presence
and behavior of the pure MnP4 capping layer. XPS results show a nitrogen
environment within the porphyrin, which differed in binding energy from the nitrogen
peak for a pure imidazole film. In the mixed films, the ATR-IR demonstrated the
addition of porphyrin alkyl and aryl environments upon substitution into the
imidazole-capping layer.
The ability of the MnP4 films to reversibly bind different axial ligands is
inferred from the activity in the Soret region of the UV-vis spectra upon heat and
solvation. It appears that the Soret Band splits into two peaks, which typically
represent the binding of a chloride ligand and the binding of either a phosphonic acid
or an imidazole ligand in the fifth and sixth coordination sites. Further, it is possible
that porphyrin domains form with slightly different ligand environments.


32
c
Figure 1.16: Porphyrin chromophore interactions: The square represents the
chromophore and its disecting axes. A) H-type or face-to-face aggregates; B) edge-to-
edge aggregates; C) J-type or head-to-tail aggregates.
The transition dipoles Mx and My are typically parallel to the plane of the
chromophore except when the nature of the metal in the chromophore center causes a
puckering of the ring. Therefore, polarized UV-vis experiments can easily indicate
orientational changes of the chromophore within a film (Figure 1.16).76-83-84
Incorporation of porphyrins into LB films is currently of interest in scientific
literature. These films are designed in order to prepare selective gas-sensors,1*74-75
photovoltaic devices,85 electron-transfer materials,72-86 molecular wires,87 and novel
heterogeneous catalyst systems.88 However, a difficulty arises in the stability of the
samples using the "typical" LB methods of purely hydrophilic/hydrophobic
interactions or by self-assembly involving tethering through a ligand. Including a
metal-phosphonate lattice into these films should significantly improve the stability
and the applicability of these materials in ultra-thin, organized films.
Typically, LB films containing porphyrin constituents have been studied in
which the chromophore itself is the polar head group. These porphyrin films have
been successfully prepared with either the molecule sufficiently diluted with a film
stabilizing amphiphile,33-88'90 such as stearic acid, or with long hydrophobic chains


56
The reaction products were studied by GC. The GC instrument was a
Shimadzu GC-17A (Columbia, MD) with a hydrogen flame ionization detector. A 1
pL portion of the reaction solution was injected onto the 25 m, 0.025 mm ID RTX-5
column (Crossbond, 5% diphenyl-95% dimethyl polysiloxane). The column was held
at 50 C for 3 min and then ramped at 10 C min'1 for 15 min.
Sensitivity factors (k) were determined using decane and o-dichlorobenzene as
the internal standards. A series of runs were performed for both the cyclooctene
(CyO) and the cyclooctene oxide (CyOO) standards. Equation 2.2 was used to
calculate k from the GC trace areas of the standard (As) and the product (ACy00) and
the known sample weights (wCy00 and ws).
'CyOO
WCyiX)^S
wsA:yoo
(2.2)
After an average k value was obtained for the CyO and CyOO, the catalysis yields
were determined from the reaction mixture using Equation 2.3:
WCyOO ~
"CyOO
WSAC
'yUO
As
(2.3)
Because the PhIO oxidant was rather insoluble, a series of 1 mL aliquots of a
1.1 g L"1 solution of PhIO in CH2C12 were dried and weighed. The final weights were
1.1 mg 9%, assuring us that the amount of oxidant in each reaction was
approximately the same.
In order to compare nearly the same concentrations of catalyst in both the
homogeneous and heterogeneous cases, the concentration of porphyrins in the films


92
That such high concentrations of ethylphosphonic acid were necessary to
induce a change in the MnPO spectrum indicates that the five-coordinate MnTPP(Cl)
structure was generally favored over the six-coordinate MnTPP(Cl)(PA) structure (PA
= phosphonic acid). However, with the four phosphonic acids linked to the MnP4
chromophore through the alkyl chains, the effective concentration of phosphonic acid
in the vicinity of the metal was very high. Therefore, MnP4 in CHC13 solutions favor
phosphonic acid axial ligation. Considering the Soret Band in the above MnP4
concentration study (Figure 4.4), it is apparent that this preference is stronger in the
more dilute solutions of MnP4.
4.2.1.4. MnP4 in solution with chloride ions. If the UV-vis peak at 460 nm
demonstrated the porphyrins propensity to bind phosphonic acids, it was important to
determine if the phosphonic acid could be replaced with another ligand such as
imidazole (ImH), or chloride. According to Arasasingham, the displacement of a
water or hydroxy ion by imidazole is encouraged by the electron-donating nature of
the nitrogen base ligand.114 Unfortunately, no literature precedence was found on the
strength of the phosphonate binding. Though chloride binding was implied in
concentration studies of MnP4 in CHC13, it was further tested by adding tetra-
butylammonium chloride, /-BuNH3+ Cl, to solutions of MnP4 at constant
concentrations of 10'5 and 10'6 M (Figure 4.6). Similar behavior was observed with
added bromide ions, with Band Vii shifted to slightly lower energies. As the chloride
concentration increased, the red shoulder at 477 nm seen in the original MnP4 spectra
in CHC13 became dominant and the blue shoulder, indicating phosphonic acid binding,
disappeared completely.


3.16Illustration of orientation and packing of PdP4 films transferred at high and
low MMA 80
4.1 Structures of A) MnP4 and B) MnPO 84
4.2 UV-vis of MnPO in CHC13 87
4.3 Solvent behavior of MnP4 in water, EtOH and CHCI3 88
4.4 UV-vis concentration study of MnP4 in CHCI3: a) 10'6 M, b) 10'5 M 88
4.5 MnPO in CHCI3 (1 x 10'7 M) with ethylphosphonic acid: a) pure MnPO,
b)1x104 M ethylphosphonic acid, c) 2 x 104 M ethylphosphonic acid,
d) 3 x 104 M ethylphosphonic acid, e) pure MnP4 90
4.6 Solution UV-vis investigation of MnP4s sensitivity to displacement of
R-PO(OH) by chloride at 1 x 10' M. The arrows indicate the changes
in the intensity of the peaks as the chloride concentration changes from
0.0 M to 0.1 M while the concentration of MnP4 stay constant in CHCI3 93
4.7 Isotherm of MnP4 on water subphase 94
4.8 Reflectance UV-vis of MnP4 on water subphase 95
4.9 UV-vis of MnP4 capping layers transferred onto ODPA/Zr at different
surface pressures (indicated by the arrows) 96
4.10 LB films of MnP4 transferred at A) 15 mN/m and B) 5 mN/m rinsed in
CHCI3 98
4.11 MnP4 transferred by LB at 0.7 mN m'1 and rinsed in CH3CN: A)
transferred from a 0.5 mg mL'1 solution 99
4.12 MnP4 transferred from 0.1 M [Cf] aqueous subphase at 4 mN m'1 100
4.13 MnP4 self-assembled from EtOH/PLO and rinsed in CHCI3. The legend
indicates the spectra after rinsing, after being left overnight and the
rinsed again over a three day period 101
4.14 SA MnP4 films with rinsing in hot CH3CN 102
4.15 UV-vis response of a SA MnP4 film during rinsing with hot CH3CN 103
4.16 UV-vis of MnP4 self-assembled films before and after rinsing in hot EtOH 104
4.17 MnP4 self-assembled from a 0.1 M chloride solution 105
x


66
Evidence of aggregation at all MMA is seen in the reflectance UV-vis spectra. Figure
3.8 shows the Soret Band as a function of MMA from greater than 120 2 molecule'1
to film collapse at 36 2 molecule'1. The Soret Band does not shift during
compression, and the Xmax of 426 nm indicates that the porphyrins are aggregated at
each stage of the isotherm.
Figure 3.7: Isotherms of PdPl, pure and mixed with ODPA (PdPl :ODPA), on a water
subphase.
A common procedure for enhancing the stability and processibility of unstable
Langmuir monolayers, and to reduce aggregation, is to mix the amphiphile of interest
with a good film-forming amphiphile.3388'90 In this pursuit, both of the porphyrins
were mixed with ODPA, which is a well-studied amphiphile that forms a liquid-
condensed phase on the water surface and easily binds to an exposed Zr-phosphonate
surface. As the percentage of ODPA is increased, the isotherms increasingly take on


79
3.3. Conclusions
The behavior of the monosubstituted and tetrasubstituted porphyrins is very
different on the water surface, and the differences are carried over to the transferred
films. Porphyrin PdPl spreads on the water surface to a limited extent. Our proposal
for how the molecules behave on the water surface is shown schematically in Figure
3.15. Optical spectroscopy indicates that PdPl aggregates, but the n-A isotherm and
X-ray diffraction from the transferred layers suggest that the aggregates are only a few
molecules thick. The aggregates are present at both high and low MMA and can be
transferred, as aggregates, onto the zirconated ODPA templates. Some molecules
from each aggregate chemisorb to the zirconated surface through zirconium
phosphonate linkages, but some are physisorbed as part of the preformed aggregates.
When exposed to hot chloroform, the physisorbed part of the film is dissolved away.
Figure 3.15: Illustration of orientation and packing of PdPl films transferred at high
and low MMA.


88
the first and second Soret Bands. The peak at 477 nm was identified as the formation
of a five-coordinate MnTPP Cl structure in the case of MnPO in CHC13, and therefore,
it clearly represented the analogous structure in MnP4 (Figure 4.2).
Figure 4.3 Solvent behavior of MnP4 in water, EtOH and CHC13.
Wavelength (nm)
Figure 4.4: UV-vis concentration study of MnP4 in CHC13: a) 10'6 M, b) 10'5 M.


4
pressure because, in effect, there is not a true monolayer, and the presence of the
amphiphile has virtually no effect on the surface tension of the subphase.20 There is
some debate on the existence of a two-dimensional gaseous state; some researchers
claim that there is always aggregates formed, which interact within the gaseous
phase.23
As the monolayer is compressed, the molecules will come in contact with one
another, and an observable rise in n occurs. In the initial region of noticeable pressure
increase, the molecules are colliding, but the film is in a fluid-like state. The
molecules have no long-range orientational order and they are not close-packed or
organized. This region is often called the liquid-expanded state (LE) (Figure 1.1).
Within the LE phase, the alkyl chains have many degrees of freedom, and gauche
conformations are observed within the chains.
The further compression of long chain fatty acid amphiphiles leads to a more
crystalline and organized monolayer. In this phase, the hydrophobic tails of the
amphiphiles adopt an overall orientational order that is maintained within the film
domains. This orientational order seeks to balance the van der Waals interactions
between the alkyl chains with the pressure applied by the barriers. Within this region,
referred to as the liquid-condensed phase (LC) (Figure 1.1), the slope of the isotherm
is very steep, meaning that the pressure goes up rapidly without much change in the
MMA. In some cases, the structure of the amphiphiles may prohibit the formation of a
close-packed monolayer regardless of the pressure, and therefore, the monolayer enters
and remains in the LE phase.15
When the monolayer cannot compress any further, additional applied pressure
from the barriers causes the monolayer to fold either over or under itself forming
collapsed regions. The collapse point is identified as the first point of deviation from
the linear slope of the LC region of the isotherm. 15>22


METALLO-PORPHYRIN CONTAINING ZIRCONIUM PHOSPHONATE
THIN FILMS: STRUCTURE AND CATALYSIS
By
CHRISTINE MARIE NIXON LEE
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
2000


139
Figure 5.21: Increase in absorbance intensity of 2918 cm'1 peak in ImODPA with SA
time.
After a layer of pure ImODPA was formed, a layer of MnP4 was self-
assembled to monitor the incorporation of the porphyrin into these films. After 1 hr,
the absorbance intensity of the va(CH2) peak leveled off at 0.016 au (as referenced to
the ImODPA monolayer), but the peak consistently appeared at 2924 cm'1. With such
a large chromophore on the exterior of the hydrophobic region, the alkyl groups would
be expected to be more dispersed and hence, show significantly lower absorbance
intensity. Also, the addition of these bulky amphiphiles would be expected to increase
the disorganization of the monolayer and shift the alkyl peaks to higher energies.
However, the absorbance intensity implies a relatively high density of alkyl chains
from the MnP4 units with only slightly more disorganization than seen in SA ODPA
films. The physisorption of the MnP4s could result in the alkyl chains burying into the
hydrophobic region of the chemisorbed film, leading to a high density of alkyl chains
along with some semblance of organization within this region. The possible


75
Wavelength (nm)
Figure 3.12: UV-vis of SA PdP4 films rinsed in hot CHC13.
3.2.3.2. Films of compound PdPl. The FI-A isotherms and the reflectance
UV-vis experiments described above indicate that the molecules of PdPl aggregate
upon spreading, and this aggregation is preserved in the transferred films. In contrast
to PdP4, the monophosphonate PdPl is only slightly influenced by attempts to break
up the aggregates by changing the deposition conditions. The UV-vis spectrum of a
capping layer of PdPl transferred at 52 2 molecule*1 (12 mN nr1) is shown in Figure
3.13, where the Soret Band appears at 426 nm, consistent with the value observed in
the reflectance spectrum taken from the water interface. The shape of the Soret Band
does not change for films deposited at higher MMA, higher temperatures, or in
mixtures with ODPA. The peak position shifts only slightly (Table 2). The
orientation of the chromophores were also unaffected by the deposition conditions.
Polarized spectra consistently give tilt angles of 90, corresponding to the porphyrins
lying flat.


87
Figure 4.2: UV-vis of MnPO in CHC13.
4.2.1.2. UV-vis of MnP4 in solution. Similar solvent shifts were observed in
the case of MnP4. In CH2C12 or CHC13 at 106 M or lower concentrations, the ^max
appeared at 463 464 nm, whereas in EtOH or water, the symmetric Soret Band
occurred at 454 nm (Figure 4.3). The peak at 454 nm corresponds to the MnPO Soret
Band in EtOFl indicating a similar axial environment, likely a bis-ethanol complex;
however, a very clear band, Va, was present at 418 nm in the MnP4 solutions.
Additionally, the ratios of Band V to VI were different for each different solvent,
implying that coordinating solvents effect the porphyrin axial environment.
The observed MnP4 spectral behavior in CHC13 was very different from the
spectral behavior in EtOH or H20. At 10'6 M, the Xmax occurs at 463 nm with a distinct
shoulder present on the red side of the Soret Band. As the concentration of porphyrin
in CHC13 increased from 10'6 M to 10'5 M, the red shoulder became a distinct second
peak at 477 nm (Figure 4.4). The two peaks are hereafter referred to as Vi and Vii for


138
solution of ImODP A for five minutes, the absorbance intensity of the va(CH2) peak
was 0.004 au, and the va(CH2) and vs(CH2) peaks appeared at 2926 cm1 and
2854 cm-1, respectively. After 20 min, the absorbance increased to 0.0065 au and the
peaks shifted to 2920 cnr1 and 2850 cm1. There was no further shift observed in
these peaks; however, the absorbance slowly increased over 2 hr, at which time the
absorbance intensity remained constant at 0.012 au. These results proved the presence
of a monolayer of ImODP A (Figure 5.20 and 5.21). However, the FWHM of 28 cm'1
was significantly greater than those seen in ODPA monolayers, indicating a level of
disorganization in these self-assembled films. A peak was also observed at 1307 cm'1,
which corresponds to the presence of ON stretches from the imidazole. Hence, ATR-
IR studies confirm the presence of a monolayer of ImODP A formed from the SA of
this amphiphile from EtOH/H20.
Figure 5.20: ATR-IR of ImODP A SA film.


169
(96) Mohajer, D Monfared, H.H. J Chem. Res. S 1998, 772-773.
(97) Arasasingham, R. D., He, G.-X., Bruice, T.C. J. Am. Chem. Soc. 1993,115,
7985-7991.
(98) Arasasingham, R. D. J., S., Bruice, T.C. J. Am. Chem. Soc. 1992,114, 2536-
2544.
(99) Baciocchi, E., Boschi, T., Galli, C., Lapi, A., Tagliatesta, P. Tetrahedron 1997,
53,4497-4502.
(100) Guo, C.-C., Li, H.-P., Xu, J.-B. J. Cat. 1999,185, 345-351.
(101) Coliman, J. P., Zhang, X., Lee, V.J., Uffelman, E.S., Brauman, J.I. Science
1993, 261, 1404-1411.
(102) Lai, T.-S., Kwong, H.-L., Che, C.-M., Peng, S.-M. Chem. Commun. 1997,
2373-2374.
(103) Gilmarten, C.; Lindsay Smith, J. J. Chem. Soc. Perkin Trans. 1995, 2, 243-
251.
(104) Miki, K.; Sato, Y. Bull. Chem. Soc. Jpn. 1993, 66, 2385-2390.
(105) Deniaud, D.; Schollom, B.; Mansuy, D.; Rouxel, J.; Battioni, P.; Bujoli, B.
Chem. Mater. 1995, 7, 995-1000.
(106) Martinez-Lorente, M. A., Battioni, P., Kleemiss, W., Bartoli, J.F., Mansuy, D.
J. Mol. Cat. A 1996,113, 343-353.
(107) Cooke, P. R., Lindsay Smith, J.R. Tet. Lett. 1992, 33, 2737-2740.
(108) Neys, P. E. F., Severeyns, A., Vankelecom, I.F.J., Ceulemans, E., Dehaen, W.,
Jacobs, P.A. J. Mol. Cat. A Chemical 1999,144, 373-377.
(109) Groves, J. T., Ungashe, S.B. J. Am. Chem. Soc. 1990,112, 7796-7797.
(110) Campestrini, S., Meunier, B. Inorg. Chem. 1992, 31, 1999-2006.
(111) Yuan, L.-C., Bruice, T.C. J. Am. Chem. Soc. 1986,108, 1643-1650.
(112) Tangestaninejad, S., Moghadam, M. Syn. Comm. 1998, 28, 427-432.
(113) Coyle, C. L., Rafson, P.A., Abbott, E.H. Inorg. Chem. 1973,12, 2007-2010.
(114) Arasasingham, R. D., Bruice, T.C. J. Am. Chem. Soc. 1991,113, 6095-6103.
(115) Boucher Coord. Chem. Rev. 1972, 7, 289-329.


CHAPTER 4
MANGANESE PORPHYRIN CONTAINING
ZIRCONIUM PHOSPHONATE THIN FILMS
4,1 Background
Monolayer and film work using the molecule manganese 5,10,15,20-
tetrakis(2,3,5,6-tetrafluorophenyl-4-octadecyloxyphosphonic acid)porphyrin, or
MnP4, will be discussed in Chapter 4 (Figure 4.1 A). For comparison, work done
using a similar molecule without the four alkylphosphonic acid chains, manganese
5,10,15,20-tetrakis(penta-fluorophenyl)porphyrin, or MnPO, will also be discussed
(Figure 4.IB). The manganese porphyrins are structurally and chemically more
complex than the palladium porphyrins. The Mn(III) central metal is a 5- or 6-
coordinate d4 metal.so,127,128 Depending on the ligand character, Mn(III) is either S =
2 (high spin) or S = 1 (low spin).129 Also, depending on the axial ligand or ligands,
the Mn(III) may or may not be co-planar with the porphyrin ligand. Mn(III) also has
an easily accessible lower oxidation state, which leads to significant metal/porphyrin
electronic interactions,80 the Mn(III)-porphyrins have a tendency to form face-to-face
dimers bridged through an axial ligand,130 and the Mn(III)-porphyrins are vulnerable
to demetallation under certain conditions. Therefore, film characterization using these
molecules was much more complicated than with the Pd-porphyrins.
To investigate the catalytic properties of manganese-porphyrin films, film
preparation procedures involving the tethering of Mn-porphyrins to a metal
83


74
9-bilayer films. It is probably poor organization in the template layer of porphyrin
PdP4 that is responsible for the lack of a well-defined layered structure.38
Mixed monolayers of PdP4 with ODPA were transferred onto ODPA templates
at different points along the surface pressure vs. area isotherms as shown in Table 1,
and the aggregation of the porphyrin in the transferred film parallels that seen in the
films of the pure porphyrins. For films transferred at pressures of 15 mN nr1, the
Soret Band appeared at 420 nm, shifting to 415 nm when transferred at pressures less
than 5 mN nr1 which, again, corresponds to the non-aggregated form seen in EtOH.
In all cases, polarized UV-vis indicates that the porphyrins orient parallel to the
surface.
The mixed monolayers show an interesting effect with increased temperature.
A mixed monolayer of 10% PdP4 with ODPA transferred at 15 mN nr1 on a subphase
heated to 40 C shows a Soret Band A.max of 415 nm, shifted from 420 nm for the same
film deposited at room temperature. As the subphase is heated, the aggregates appear
to break-up in the mixed film. A similar effect is not seen on the pure films of PdP4.
It appears that the ODPA plays a role in breaking up the aggregated domains at higher
temperatures.
Films of PdP4 were also prepared by the SA technique. After the zirconated
ODPA template had been exposed to a PdP4 solution in EtOH/H20 for 2 hr, the
porphyrins were successfully incorporated into these films. The Soret Band appeared
at 414 nm, which then shifted to 411 nm after 60 min rinsing in hot CHC13. The A,max
in the SA film was the closest of any of the PdP films to that seen in the dilute
solution. Therefore, it appears that non-aggregated assemblies of PdP4 are easily
obtained by self-assembly (Figure 3.12). However, the overall absorbance intensity of
these non-aggregated films is lower than observed in the films transferred by the LB
technique at high MMA.


34
reach of the oxygen atom on the metal. After the oxygen has been successfully
transferred to the substrate, the product is released and the catalyst is regenerated.93
Manganese porphyrins are probably most well known as epoxidation and
hydroxylation catalysts whether under heterogeneous or homogeneous conditions.
The manganese porphyrin catalysts can utilize a number of different oxidants such as
iodosylarenes, alkylhydroperoxides, hydrogen peroxides, and perchlorates among
others, in order to accomplish the facile oxidation of deactivated olefins, alkanes,
alcohols, ethers, and amines.97'100 A hyper-valent metal-oxo species is believed to be
the active intermediate in the oxidation process in cases such as dioxygen activation of
Cytochrome P-450, or in oxygen transfer from iodosylbenzene, peracids, or
hypochlorite oxidants.101 Though there is some debate on the actual mechanism of the
epoxidation, there are a few possible routes (Figure 1.17). The suggested first and
rate-determining step is the formation of a charge-transfer complex. Whether the
reaction then proceeds through epoxidation or rearrangement is dependent on the
oxidation potentials of the alkenes and the oxidants, steric and electronic structures of
the reactants, and the ability of the substrates to undergo rearrangement.97
Porphyrins have also been studied in chiral catalysis. Lai and co-workers studied
the asymmetric aziridation of alkenes using a chiral manganese porphyrin catalyst.102
They found that with bulky chiral substituents on the porphyrin, successful nitrene
transfer to alkenes was achieved. Enantiomeric excess ranging from 43 to 68% and
product yields greater than 70% were obtained. In these catalysis studies, the reactive
intermediate was a Mn(IV) complex.


98
the phosphonate ligation was not as reversible when the films were transferred at
higher pressures.
Figure 4.10: LB films of MnP4 transferred at A) 15 mN/m and B) 5 mN/m rinsed in
CHC13.
When LB films of MnP4 transferred at 300 2 molecule'1 (0.7 mN m'1) were
rinsed only in hot CH3CN, the band at 477 nm (Band Vii) was again observed (Figure
4.11). The Soret Band at 464 nm corresponding to phosphonate binding conversely
disappeared. These results suggest that hot solvents were able to eliminate the
phosphonic acid binding leading to the stable five-coordinate MnTPP(Cl) structure,
and that the appearance of this structure is not a result of chromophore aggregation.


131
Figure 5.14: ImODPA/MnP4 self-assembled from 70/30 mixture and rinsed in hot
CHC13.
5.3.4. Other methods for preparing ImODPA and MnP4 containing films.
5.3.4.1. LB deposition of MnP4 followed by substitution of ImODPA. Films
of MnP4 were transferred from a water subphase at 5, 10, and 15 mN m'1 (before,
during and after the plateau region of the isotherm shown in Figure 4.7). ImODPA
was substituted into these films from an EtOH/H20 solution. It was thought that, if
the MnP4 could form a complete monolayer with phosphonic acids bound to the
zirconium network prior to imidazole being present, it may be more likely that there
would be imidazole binding instead of phosphonic acid binding the central metal. The
UV-vis behavior of these films after the substitution of ImODPA and after rinsing
with CH2C12 at room temperature is shown in Figure 5.15. Unfortunately, there are


70
The extremely well organized and oxophilic surface allows deposition of almost any
phosphonic acid monolayer, including those that are not stable monolayers and would
normally not transfer. Monolayers of PdP4 and PdPl were transferred at a range of
temperatures, pressures and subphase pHs (Tables 1 and 2). Films of the porphyrins
mixed with ODPA were also transferred under a variety of conditions. Under some
conditions, perfect, organized monolayers were obviously not formed, but the films
could be transferred onto solid supports and studied.
3.2.3.1 Films of compound PdP4. To form alternating films of PdP4, the
Langmuir monolayers were transferred as capping layers onto zirconated ODPA
template layers. Films were transferred at different surface pressures and the Soret
Band of the transferred films was used to monitor differences in chromophore
aggregation in the deposited films. The UV-vis spectrum of a film transferred at 130
2 molecule1 (15 mN nr1) is shown in Figure 3.11, where the Xmax of the Soret Band
appears at 420 nm, significantly red-shifted from any of the solution spectra of PdP4.
The red-shift suggests increased aggregation, which is expected because at such a
small MMA, the chromophores must be either tilting perpendicular to the surface and
organizing side-by-side, or sliding over one another to form bilayers or multilayers.
Polarized UV-vis spectroscopy indicates the porphyrins are oriented parallel to the
surface, implying the latter arrangement.
Layers of PdP4 were also transferred at 190 (12mN nr1) and
300 2 molecule1 (Figure 3.11). The Soret Band shifts to 418 nm for the film
transferred at 190 2 molecule1 and to 416 nm for the film transferred at 300 2
molecule1, indicating less aggregation in films transferred at high MMA. At these
larger MMA, the porphyrin chromophores should be lying flat at the air-water
interface with little aggregation and they appear to remain non-interacting when
transferred.


149
has reverted back to its peak energy at 460 nm. From the known mechanism of this
epoxidation reaction, the porphyrin loses its axial ligand and becomes oxidized;
therefore, there is evidence for this ligand exchange, which is witnessed in the UV-vis
of the films after the catalysis (Figure 6.1).
When this same reaction was run for only 2 hr, the overall yields, as expected,
decreased (Table 6.1). These films were prepared in the same manner, as were the
films studied in the previous catalysis experiment. The ratio of Bands V:VI changes
slightly, as the axial ligand environment is not identical in both cases. Again, the UV-
vis behavior before and after the catalysis reaction was studied and is shown in Figure
6.2.
Figure 6.2: SA MnP4 film before and after 2 hr. catalysis run with 40:5:20
cyclooctene: PhIO:decane in CH2C12.


91
demetallation of the manganese porphyrin. This peak was observed in the absence of
any strong oxidants indicating that this peak is probably not representing oxidation
products.
The electronic spectra of Mn(III)TPP Cl in DMSO was presented by Hansen
and Goff.129 The high spin moiety that was formed by the coordination of the DMSO
solvent molecules showed a sharp Soret Band at 465 nm with two prominent higher
energy bands at 375 and 397 nm. However, when the molecule was converted to a
low-spin Mn(III)-porphyrin complex by the bis-axial ligation of imidazolate anions,
the Soret Band shifted to 451 nm and broadened. Also, the band at 397 nm increased
in intensity.129 In a similar way, the phosphonic acid or phosphonate may have been
behaving like the imidazolate anion and converting the MnPO from a high spin to a
low spin complex. The spin-state of MnPO in solution was studied using the Evans
method (described in Chapter 2). The NMR results indicated that the MnPO with and
without phosphonic acid ligands were in the same spin-state, therefore, the observed
spectral behavior was due only to the ligand environment of the porphyrin.
The peak at 418 nm aligned with the Soret Band of the corresponding free-base
porphyrin in CHC13 (s = 9.0 x 106). The strong attraction between manganese and
phosphonates is well known; therefore, irreversible binding of the phosphonate to the
manganese may result in the demetallation of the porphyrin. The demetallation could
be facilitated by the protic nature of the phosphonic acid. This band was often
observed, but its relative intensity was not consistent.
When the MnPO/ethylphosphonic acid solution spectra were overlayed with a
solution spectrum of pure MnP4, the red shoulder, Band Vii of the MnP4 spectra,
aligned with the original MnPO peak. Also, the blue shoulder, Band Vi, which
emerged with the addition of the ethylphosphonic acid to a MnPO solution, was similar
in energy to the original MnP4 peak.


122
i I i I i I i I i I '
350 400 450 500 550 600 650
Wavelength (nm)
Figure 5.7: MnP4 substituted onto a 25% ImODPA/HDPA film, rinsed in room
temperature and hot CHC13.
When the film was then exposed to hot CHC13, the absorbance intensity
decreased further and the red component of the Soret Band appeared at 477 nm.
Therefore, physisorbed chromophores can be eliminated from the surface by using
room temperature or hot solvents, but a change in the axial environment was only
associated with rinsing in hot solvents. The band representing halide binding at ca.
477 nm was not permanent and relaxed back to the original peak at ca. 460 nm after 24
hr (Figure 5.8).


REFERENCES
(1) Papkovsky, D. B. Sensors and Acts. B: Chem. 1995,1-3, 213-218.
(2) Jung, G. Y., Pearson, C., Kilitziraki, M, Horsburgh, L.E., Monkman, A.P.,
Samuel, I.D.W., Petty, M.C. J. Mater. Chem. 2000,10, 163-167.
(3) Ogata, N. Makromol. Chem.-Macromol. Symp. 1992, 53, 191-200.
(4) Papkovsky, D. B., Ovchinikov, A.N., Ponomarev, G.V., Korpela, T. Anal. Lett.
1997, 30, 699-719.
(5) Fabianowski, W., Jaccodine, R., Kodnani, R., Pearson, R., Smektala, P. Adv.
Mat. Opt. Elec. 1995, 5, 199-213.
(6) Papkovsky, D. B., Desyaterik, I.V., Ponomarev, G.V., Kurochkin, I.N.,
Korpela, T. Anal.Chim.Acta 1995, 310, 233-239.
(7) Aramaki, K. Corrosion Sci. 1999, 41, 1715-1730.
(8) Arnold, D. P., Manno, D., Micocci, G., Serra, A., Tepore, A., Valli, L. Thin
Solid Films 1998, 327-329, 341-344.
(9) Penza, M., Milella, E., Anisimkin, V.I. IEEE T. Ultrason. Ferr. 1998, 45,
1125-1132.
(10) Kauffman, F., Hoffman, B., Erbach, R., Heiliger, L., Siegmund, H.U., Volker,
M. Sensors and Acts B-chemical 1994,18, 60-64.
(11) Marlow, A. L., Davis, J.T. Tet. Lett. 1999, 40, 3539-3542.
(12) Petrucci, M. G. L.; Kakkar, A. K. Chem. Mater. 1999,11, 269-276.
(13) Suh, J. H Hong, S.H. J. Am. Chem. Soc. 1998,120, 12545-12552.
(14) Agarwal, V. K. Physics Today 1988, 40.
(15) Roberts, G. G. Langmuir-Blodgett Films', Plenum Press: New York, 1990.
(16) Langmuir, I. J. Am. Chem. Soc. 1917, 39, 1848-1906.
(17) Blodgett, K. A.; Langmuir, I. Phys. Rev. 1937, 51, 964.
(18) Levine, O., Zisman, W.A. J. Phys. Chem. 1957, 61, 1068.
164


33
attached to the chromophore to stabilize the monolayer on the water surface.84-91
There are significant disadvantages to this method of film preparation. First, the
chromophore is buried in the film interior on a transfer onto a hydrophilic substrate,
and commonly, the hydrophobic interactions necessary to deposit onto a hydrophobic
substrate are too weak for successful transfer. Also, the hydrophilic interactions are
typically of a hydrogen-binding nature making this a relatively weak interaction
destabilizing the film. Finally, the conditions necessary for transferring the traditional
porphyrin LB films facilitate aggregate formation, which can be detrimental in certain
applications, such as catalysis.
The aggregation, or chromophore n-n interactions, is often a consequence of
the film forming procedures. First, compression of the film on the water surface
forces the eventual overlap or tilting of the chromophores.84-88-90 Also, the decreased
affinity of the derivatized chromophores for water tends to force the chromophores to
aggregate rather than to spread on the water surface.92 Understanding the molecular
orientation, aggregation, and morphology of porphyrin LB films is critical because
each is intimately linked to chromophore behavior. For example, aggregation can
significantly reduce or eliminate the efficiency of the porphyrin in catalysis76 or the
ability of the porphyrin to bind probe molecules in a sensor.92 Therefore, it is
desirable to find methods for forming porphyrin LB films with no aggregation.
1.3.2. Background on Manganese Porphyrins
Biomimetic systems involving porphyrin catalysts have often been discussed in
scientific literature over the past 20 years. Manganese and iron porphyrins are
commonly studied oxidation catalysts and are prevalent elements in biological
processes.93-96 Biochemical oxidation reactions employing metallo-porphyrins
involve reversible site-specific binding of the substrate such that the substrate is within


24
1.3 Background on Porphyrins
1.3.1 Optical Behavior of Porphyrins
Porphyrins are a common research focus in physics, chemistry, and biology.
Physical and chemical interest in porphyrins stems, for example, from their highly
conjugated structure that allows facile electron-transfer,68-72 and from their chemical
activity at an exposed metal that may be active toward catalysis or chemical
sensing, f873-75 Biologists and biochemists are interested in the common biological
building blocks that are based on the porphyrin structure.76-78
The core structure of the porphyrin is the completely saturated porphine
macrocycle (Figure 1.11).79 Upon reducing this macrocycle to the unsaturated form,
the porphyrin chromophore is achieved. By hydrolyzing one of the pyrrole units, the
chlorin compound is prepared. Another important structure based on the porphine
core is the phthalocyanine or the tetraazatetrabenzporphyrin. Each of these structures
includes either two protons, as in the free base porphyrin, or a coordinated metal
within the center of the porphyrin, called the metallo-porphyrin. Examples of
biologically active porphyrins include chlorophyll, which is a manganese-coordinated
chlorin molecule, and heme, which is an iron-substituted porphyrin.


104
460 nm to 477 nm was consistently observed. However, when these films were rinsed
in hot EtOH, an anomaly occurred. Instead of the increase in the band at 477 nm, as
was so commonly observed in CHC13 and CH3CN, now a peak to the high-energy side
of the original band at 454 nm grew in intensity. This peak aligns with the band seen
for the MnP4 and MnPO in EtOH solutions, indicating that in the films, domains of the
chromophores bind EtOH and therefore experience mobility in the axial positions
(Figure 4.16).
Figure 4.16: UV-vis of MnP4 self-assembled films before and after rinsing in hot
EtOH.
4.2.4.2. MnP4 Self-assembly from chloride solutions. To avoid phosphonic
acid ligating the porphyrin central metal and to promote the phosphonic acid binding
to the zirconium network, the MnP4 was self-assembled out of a 1.4 x 1 O'5 M solution
of porphyrin that was 0.1 M in /-BuNH3+ Cl'. Following a successful self-assembly,


BIOGRAPHICAL SKETCH
Christine M. Nixon Lee was bom in Dayton, Ohio, on February 17, 1973. She
moved with her family to Mansfield, Ohio, in fifth grade, and she graduated from
Lexington High School in June of 1991. Christine entered Baldwin-Wallace College
in Berea, Ohio, in September 1991 as a music major, and in the fall of 1992, she began
her chemistry major. Christine graduated from Baldwin-Wallace College summa cum
laude in June of 1995 with a B.S. in chemistry and a minor in music.
In the summer of 1995, she started studying at the University of Florida, and
joined Dr. Dan Talhams group in the spring of 1997-just in time to do her oral
qualifying exam. She married Lawrence Lee in July of 1999, and will be joining him
in New York City after she graduates in the spring of 2000 with her Ph.D. in
chemistry.
171


16
metal halide surfaces.37 Many of the surfactants studied by self-assembly did not form
stable monolayers on aqueous subphases, and therefore, could not be studied by the
LB method. However, these surfactants were easily studied by the SA method.
1.2. Hybrid Organic/Inorganic Ultrathin Films Based on Layered Solids
1.2.1. Background
A new class of LB films has been developed, which incorporate an inorganic
metal phosphonate network into the polar region.2838*41 These films, which can
contain a variety of organic groups and metals, were inspired by and show analogous
behavior to their solid-state metal phosphonate analogues. In addition, these films are
more stable than typical fatty-acid based LB films, and the inorganic lattice provides
potential function.42
The metal phosphonate solid-state materials are attractive because they can be
prepared at low temperatures from aqueous solutions. Further, the structures can
provide a model system to which the film properties can be compared. Due to the
structure of the metal lattices, which directs the film formation, the orientation and
packing of the alkyl region is predictable.
Metal phosphonate materials are especially interesting due to their potential
applications in the areas of sorbents43 and catalysts,44 and because of their layered
structures, these materials can be used as intercalation compounds.45*49 The interest in
the metal phosphonates was sparked by their potential as inorganic ion exchange
materials;50*52 however, the organic region can also be modified and functionalized,
providing a straightforward method for preparing a wide variety of materials.


118
this manner was well-organized and represented the most compact, and therefore most
challenging, bilayer for MnP4 substitution.
With the potential phosphonic acid binding sites in the Zr-network occupied
with HDPA, the phosphonic acid tethers on the porphyrin were available for
intramolecular ligation. From solution results, however, chloride or bromide could
displace these phosphonic acid axial ligands (Figure 5.4). When the substituted film
was studied by UV-vis immediately after the MnP4 SA process was complete, the
appeared at 454 nm. At such a high energy, the Soret Band implied that the
chromophores were aggregating. Two lower energy shoulders could also be
identified in the broadened Soret Band. The first appeared at ca. 463 nm, which may
represent non-aggregated porphyrin domains, and the second appeared at ca. 478 nm at
lower intensity indicating the presence of MnTPP(Cl) moieties.
The film stability was examined by exposure to hot CHC13 and a loss in
absorbance intensity and a significant peak broadening was observed. After the first 5
min in hot CHC13, no further decrease in the overall absorbance intensity of the film
was perceived, and this spectrum represented only the chemisorbed porphyrins. With
the physisorbed chromophores removed, the original red shoulder at 478 nm, which
was also observed previously in the solution and films of pure MnP4, was more
distinct, and there appeared to be two peaks, Bands Vi and Vii. From the two apparent
Soret Bands, it seems that the remaining porphyrins were either MnTPP(Cl)(PA) (peak
at 463 nm) or MnTPP(Cl) (peak at 478 nm) (Figure 5.5).
Due to the splitting and broadening of the Soret Band, it is impossible to
attribute a change in absorbance intensity just to removal of physisorbed
chromophores. Some physisorbed chromophores were indeed removed, which was
found by calculating the differences in peak areas before and after rinsing. Figure 5.5
also reveals a decrease in the absorbance intensity ratio of Band V to Band VI. A


I certify that I have read this study and that in my opinion it conforms to acceptable
standards of scholarly presentation and is fully adequate, in scope and quality, as a dissertation
for the degree of Doctor of Philosophy.
Associate Professor of Chemistry
I certify that I have read this study and that in my opinion it conforms to acceptable
standards of scholarly presentation and is fully adequate, in scope and quality, as a dissertation
for the degree of Doctor of Philosophy.
/illiam Weltner
Professor of Chemistry
, (aJjJSZ*.
I certify that I have read this study and that in my opinion it conforms to acceptable
standards of scholarly presentation and is fully adequate, in scope and quality, as a dissertation
for the degree of Doctor of Philosophy. ^
.
Martin Vala
Professor of Chemistry
I certify that I have read this study and that in my opinion it conforms to acceptable
standards of scholarly presentation and is fully adequate, in scope and quality, as a dissertation
for the degree of Doctor of Philosophy.
fit (~) h
Kenneth Wagener
Professor of Chemistry
I certify that I have read this study and that in my opinion it conforms to acceptable
standards of scholarly presentation and is fully adequate, in scope and quality, as a dissertation
for the degree of Doctor of Philosophy.
Professor of Agricultural and Biological
Engineering
This dissertation was submitted to the Graduate Faculty of the Department of
Chemistry in the College of Liberal Arts and Sciences and to the Graduate School and was
accepted as partial fulfillment of the requirements for the degree of Doctor of Philosophy.
August 2000
Dean, Graduate School


155
Table 6.3: Conversion of cyclooctene to cyclooctene oxide with varying cyclooctene
to PhIO ratios in lmL of solution using MnP4 SA films over 24 hr.
Experiment
Cyclooctene
Oxide Yield
Turnovers
Bleaching
60:5:20
Blank
3%
Homogeneous
7%
350
Films
20%
1000
<15%
20:5:20
Blank
2%
Homogeneous
5%
250
Films
18%
900
<15%
6.2.1A Oxidation dependence on presence of heterocyclic ligand. Addition of
an imidazole heterocyclic ligand is commonly reported to enhance the catalytic
behavior of Mn-porphyrins in the presence of a peroxide oxidant. However, little was
mentioned in the literature about the porphyrin response to this ligand when using PhIO
as the oxidant. The imidazole was not only expected to encourage the heterolytic
cleavage of the 0-0 bond of the peroxides but also to stabilize the oxidized manganese
state; therefore, some extent of catalysis improvement might be expected. To examine
this sensitivity, a SA ImODPA/SA MnP4 film was prepared and rinsed to remove
physisorbed chromophores. Using a 40:5 substrate to PhIO ratio, the catalysis reaction
was run over 24 hr (Table 6.4).


69
Figure 3.10: Mean molecular area vs. ratio of ODPA/Porphyrin: A) PdP4, B) PdPl.
If the ODPA diluent were breaking apart the preferred organization of the
porphyrins in the films, Spor would increase as the aggregates separate. The decrease
in Spor in the mixed films suggests that either the porphyrin chromophores are
reorienting in the mixed films or aggregation actually increases in the mixed films.
However, it does not appear that porphyrin aggregation decreases in the mixed
monolayers.
3.2,3 Langmuir-Blodgett Films
LB films of PdP4 and PdPl were prepared using the deposition procedure
described in Figure 2.2. The stepwise deposition allows fabrication of both symmetric
films, where the template and capping monolayers are the same, and alternating films,
where the two monolayers in the bilayer are different. Both types of films were
prepared for each porphyrin (Figure 3.2). It has been shown that a zirconated ODPA
template layer frequently provides the best substrate for transferring a capping layer.65


45
STEP 1
STEP 2
Figure 2.2: Schematic of the three-step deposition process used for zirconium
phosphonate films.


125
for its bulky nature, which should prevent its binding to the porphyrin. Rinsing the
films in /-BuNH2 caused a blue shift in the Soret Band from 461 nm to 458 nm, which
was therefore, assigned to imidazole binding to the central metal. It was unclear if
imidazole binding was encouraged by deprotonation or if the elimination of some
physisorbed and therefore, non-imidazole bound porphyrins made it easier to observe
the imidazole binding. Because of the film structure, the complex is most likely a 6-
coordinate MnTPP(Cl)(Im) system.
After rinsing with hot CHC13, the Soret absorbance intensity decreased
significantly. Band Vii shifted to 477 nm, which was again associated with the
formation of the five-coordinate MnTPP(Cl). Twenty-four hours after rinsing, the
halide-binding peak at 477 nm was no longer detected. Instead, the band at 465 nm
increases in intensity as the films were left to reorganize overnight as was observed in
the pure MnP4 films. From the energy of the band at 465 nm, which is at lower
energies than the Soret Band observed with imidazole binding, this peak was likely
due to the binding of phosphonic acid ligands and not imidazoles (Figure 5.10). The
Soret Band absorbance in this film was comparable to that of previous examples of
pure MnP4 substituted imidazole films, implying roughly the same number of
chromophores were present.


54
The solid was collected and washed with another 100 mL aliquot of H20. The solid
was filtered again, and washed with CHC13 2 times in a beaker and filtered. The solid
was dried in a vacuum desiccator. The products melting point corresponded well to
the literature value of 210 C. Iodometric titration, involving converting the PhIO
product to Phi and I2 with HI and titrating with sodium thiosulfate, gave a purity of
99%. 122
PhIO (27.5 mg, 125 pmol) was diluted in 25 mL CH2C12. The PhIO compound
was only slightly soluble in CH2C12, so it was diluted and then sonicated for at least 30
min. After sonicating, an amount of the cyclooctene was added and the mixture was
stirred for about 1 min. Decane (97 pL, 500 pmol or 24 pL, 125 pmol), the internal
standard, was also added with stirring. lmL samples of this mixture were used for
both a blank run and a homogeneous run. In all homogeneous experiments, 1 pL of a
1 mM solution of MnPO was added to the blank solution to investigate the epoxide
yields with the porphyrin in solution.
Figure 2.3: Schematic of catalysis cell, side view.


141
Wavenumber (cm'1) Wavenumber (cm'1)
Figure 5.22: ATR-IR of alkyl region of: A) MnP4 substituted on a 100% ImODPA
base capping layer, B) MnP4 substituted on a 25% ImODPA base capping layer.
5.4 Conclusions
Thin films containing both the MnP4 and the imidazole on the surface of a
zirconium phosphonate film have been successfully prepared by a variety of methods.
The imidazole is present in the films for the purpose of acting as a heterocyclic ligand
to promote the catalytic behavior of the MnP4 chromophore. Because of the
flexibility of assembling the zirconium phosphonate thin films, the procedure for
preparing these films has been varied to optimize the incorporation of ImODPA and
MnP4. Though aggregation is difficult to identify due to the strong optical influences


29
metal-ligand charge transfer (MLCT) mixed with the porphyrin h-t* transitions even
within the Soret Band. The MLCT Bands can be porphyrin to metal, metal to
porphyrin, or even axial ligand to metal. Due to the spectral sensitivity to
chromophore substituents, to the metal its oxidation state, and to the nature of the axial
ligand, and the additional UV-vis Bands, hyperporphyrin spectra are much more
difficult to analyze.80-81
The d-type hyperporphyrins include metals of groups six through eight.
Mn(III)-porphyrin, for example, is d4 and S = 2, or high-spin, and is a characteristic d-
type porphyrin. In chloroform, Mn(III) tetraphenylporphyrin shows six peaks. An
early researcher of the Mn-porphyrins, Boucher, termed these peaks by Roman
numerals going from low to high energy. The first two peaks are in the far-red region
between 800 and 650 nm. Bands III and IV absorb in a region similar to the Q-Bands
in regular porphyrins, between 500 and 650 nm. Band V is similar to and often called
the Soret Band though this band now includes contributions from metal to ligand
mixing. Band VI is typically around 350 nm. The ratio of Bands V and VI is very
sensitive to axial ligands and ring substituents. These bands are due to porphyrin to
metal charge transfer alu(7t), a2u(7i) to eg(d7i), which implies a necessity for one or more
vacancies in the eg(d7t) orbital of the metal and reduction potentials which are not too
negative.80-81
Finally, pseudonormal hyperporphyrins include VO(IV), Cr(II), Mn(II),
Mo(IV), La and Ac where S 0. These metals show normal absorption spectra with a
weak extra absorption possible in the far-red region. All of these metals have a
partially filled or empty eg(d7i) orbital, but charge-transfers from the porphyrin to the
metal are too high in energy to be observed in the UV-vis region. In addition, further
reduction takes these metals to unstable oxidation states which makes this an even
higher energy transition and highly unlikely 80-81


100
Figure 4.12: MnP4 transferred from 0.1 M [Cl ] aqueous subphase at 4 mN m1.
4,2.4. Self-Assembled films of MnP4
4.2.4.1. Self-assembly from pure solvent. MnP4 films self-assembled from
EtOH/H20 (9/1 mixture) or CH2C12 showed a Soret Band at lower energies than
observed in MnP4 LB films. The Xmax was now at ca. 463 464 nm, which
corresponds to the peak in MnP4 solutions and in LB films after rinsing off
physisorbed and aggregated chromophores. Therefore, this peak has been attributed to
phosphonic acid binding to non-aggregated metallo-porphyrins. When self-assembled
films of MnP4 were rinsed in hot CHC13, the red Soret Band associated with the
MnTPP(Cl) increased significantly, and the peak associated with the six-coordinate
MnTPP(Cl)(PA) decreased, again proving that hot solvents can remove the
phosphonic acid ligands leaving the chloride ligand intact.


57
was calculated to be, at most, 1 nmol. In was, however, difficult to keep this
concentration constant. In the homogeneous reactions, 1 nmol of the corresponding
non-amphiphilic MnPO was used.
Imidazole is reported to improve the catalytic efficiency of the Mn-porphyrins
in the presence of a peroxide oxidant, but for comparison, we also tried to see if
imidazole would improve the catalytic efficiency in the presence of PhlO. For this
experiment, 0.1 pmol of ImH was added to the blank and homogeneous solutions
using a PhlO solution with 40 pmol CO, 5 pmol PhlO and 20 pmol decane. Also,
films prepared by SA ImODPA and SA MnP4 were used in the flow cells with this
same PhlO solution. The reactions were, again, stirred for 24 hr.
2.3.2 Catalysis using peroxide oxidants
In studying the catalysis of the epoxidation of cyclooctene (CyO) with H202,
many different substrate to oxidant ratios were studied. The epoxide yields were
greatest, however, when very dilute solutions of reactants were used to keep the
proportion of reactants to catalyst near a factor of 10 and the substrate was used in
excess. The starting materials, CyO and H202, were dissolved in 250 mL of CH2C12
with o-dichlorobenzene as the internal standard. lmL aliquots of this solution were
used for the reaction blank and homogeneous reactions and contained 8 pmol CyO,
0.2 pmol H202, and 0.2 pmol of o-dichlorobenzene. To the homogeneous reaction
were added 0.4 pmol ImH and 0.001 pmol of MnPO. The original solution was
pumped into the flow cells using the peristaltic pump, and these reactions were
allowed to stir for 24 hr at room temperature.


4.18 XPS of MnP4 SA film. The insert is an enlarged view of the same spectrum
between 200 and 80 eV 106
5.1 Structures of A) MnP4, B) MnPO, C) ImODPA and D) ImH 110
5.2 Simplified Schematic of MnP4 and ImODPA incorporation in films 111
5.3 Solvent response of A) MnPO and B) MnP4 to ImH 114
5.4 Solvent response of A) MnPO and B) MnP4 to ImODPA. Legends indicate
the molar ratio of MnP to ImODPA 116
5.5 UV-vis of ODPA/Zr/HDPA, SA MnP4 film rinsed in hot CHC13 119
5.6 MnP4 substituted onto ImODPA:HDPA LB films after CHCI3 rinsing 121
5.7 MnP4 substituted onto a 25% ImODPA/HDPA film, rinsed in room
temperature and hot CHCI3 122
5.8 UY-vis of an ImODPA/ MnP4 film after drying 123
5.9 MnPO attached to a 25% ImODPA/HDPA LB film and rinsed in hot CHC1 124
5.10 MnP4 substituted onto a pure ImODPA SA film 126
5.11 Reversibility of the chloride/phosphonic acid binding 127
5.12 MnP4 substituted film rinsed in chloride and t-butylamine solutions 128
5.13 MnP4 substituted from a 0.1 M Cl- solution onto an ImODPA layer, and
compared to an MnPO solution with ImH binding 129
5.14 ImODPA/MnP4 self-assembled from 70/30 mixture and rinsed in hot
CHCI3 131
5.15 ImODPA substituted into a MnP4 LB film transferred at 10 mN m'1 132
5.16 LB film of MnP4/ImODPA transferred from a 25/75 mixture on an aqueous
subphase, pH 11.3 133
5.17 XPS multiplex scan over the Nis region of A) ImODPA, and B) MnP4 self-
assembled films. The dashed line represents the Gaussian peak fit 134
xi


107
at 460 464 nm, which has been attributed to formation of a six-coordinate
MnTPP(Cl)(PA) structure. Also, a band at 376 nm was assigned to Band VI, and
Band Va at 418 nm was identified as corresponding to the presence of free-base
porphyrins in the films. Further, rinsing in a solvent that can eliminate the
intramolecular binding of phosphonic acid causes the Soret Band to shift to ca. 477 nm
representing the five-coordinate MnTPP(Cl). This shift is most pronounced in
solutions in which chloride ions have been added indicating that excess chloride
prevents the binding of the phosphonic acid.
The band representing phosphonic acid binding demonstrated some reversibility.
After films of MnP4 were rinsed in CHC13 or CH3CN, the structure was that of
MnTPP(Cl). When these same films were left to structurally relax, the UV-vis
showed the reappearance of the band representing the MnTPP(Cl)(PA), accompanied
by a decrease in the intensity of the MnTPP(Cl) peak. When the chromophores were
adhered to the zirconated ODPA network by less than four of the phosphonic acid
tethers, the non-bound phosphonic acid groups remained in central metals vicinity.
Therefore, displacement of the phosphonic acid ligands with hot solvents does not
prevent them from re-ligating as the film conditions change.
The SA MnP4 films have Soret Band absorbance intensities consistently between
0.015 to 0.02 absorbance units. This absorbance intensity corresponds to the LB films
transferred at MMA just before the plateau region. When the porphyrin surface
coverage is incomplete, as in the LB films transferred below 5 mN m'1 and in the films
self-assembled for very short times, the absorbance intensity was consistently around
or below 0.01 absorbance units. Therefore, depending on the deposition conditions,
the amount of chromophore incorporated into the films is reasonably consistent.
Consistency in the chromophore loading is helpful in employing these films in
catalysis studies.


2.1 Schematic of Langmuir-Blodgett trough and monolayer 42
2.2 Schematic of the three-step deposition process used for zirconium
phosphonate films 45
2.3 Schematic of catalysis cell, side view 54
2.4 Schematic of catalysis cell, top view 55
3.1 Structures of A) PdP4 and B) PdPl 59
3.2 Schematic of Pd-porphyrin films formed: a) alternating ODPA/Zr/PdP,
b) alternating ODPA/Zr/PdP:ODPA mixed film, c) symmetric
PdP/Zr/PdP, d) symmetric PdP:ODPA/Zr/PdP:ODPA 60
3.3 Solution UV-vis of Pd-porphyrins in CHC13: A) PdP4, B) PdP 1 62
3.4 Solution UV-vis of PdP4 in EtOH and water compared to CHCI3 63
3.5 Isotherms of PdP4, pure and mixed with ODPA (PdP4:ODPA), on a
water subphase 64
3.6 Reflectance UV-vis of PdP4 on water subphase 65
3.7 Isotherms of PdPl, pure and mixed with ODPA (PdPl: ODPA), on a
water subphase 66
3.8 Reflectance UV-vis of PdPl on water subphase 67
3.9 Reflectance UV-vis of 10% PdP4: 90% ODPA on a water subphase 68
3.10 Mean molecular area vs. ratio of ODPA/Porphyrin: A) PdP4, B) PdPl 69
3.11 Transmission UV-vis of PdP4 films transferred at high and low MMA.
Absorbance scale corresonds to the film transferred at 300 2 molecule'1 72
3.12 UV-vis of SA PdP4 films rinsed in hot CHCI3 75
3.13 Transmission UV-vis of films of PdPl transferred at high and low MMA 76
3.14 Absorbance of Soret vs. time rinsed in hot CHCI3: A) PdP4, B) PdPl 78
3.15 Illustration of orientation and packing of PdP 1 films transferred at high and
low MMA 79
IX


44
zirconium solution, the substrate was removed from the vial and rinsed with water.
After the template layer was successfully prepared, it was dried and characterized
independently by ATR-IR, XPS, and UV-vis if needed.
Capping layers were prepared by a variety of methods, which will be described
for each different film type in Chapters 3, 4 and 5. LB or SA methods could be used
to form the capping layers. To form the capping layer and complete the zirconium
phosphonate bilayer by the LB technique, the now hydrophilic substrate was lowered
into the trough, a monolayer was spread on the surface and compressed to the desired
pressure, and the substrate was raised through the monolayer at 5 mm min'1. To form
the capping layer by self-assembly, the hydrophilic surface was submerged in a
solution of the desired molecules at about 1 O'5 M in an appropriate solvent, usually
EtOH/H20 (9/1). The capping layer was then allowed to self-assemble.
2.1.1.2. Materials and Methods. Materials used to prepare the porphyrin
containing films included octadecylphosphonic acid (ODPA), zirconyl chloride
(Zn0Cl-8H20), and the porphyrins themselves. The porphyrins were provided by
Bruno Bujoli, Fabrice Odobel, Karine LeClair, and Laurent Camus from the
Laboratoire de Synthese Organique, at the Faculte des Sciences et des Techniques de
Nantes in Nantes, France. ODPA was used as purchased from Alfa Aesar (Ward Hill,
MA). Zirconyl chloride, 98% was used as supplied from Aldrich (Milwaukee, WI).
Octadecyltrichlorosilane (OTS) 95%, used to silanize and hence hydrophobicize the
substrates, was also used as purchased from Aldrich. Amylene stabilized HPLC grade
CHClj was used as a spreading solvent, and was used as received from Acros
(Pittsburgh, PA) and Fisher Scientific (Pittsburgh, PA).
A KSV 2000 system (Stratford, CT) was used in combination with a
homemade, double barrier Teflon trough for the Langmuir monolayer studies and LB
film preparation.


17
1.2.1.1. Zirconium Phosphonate solids. Clearfield published early work on
metal phosphonates and phosphates in the 1960s.53 The focus at this time was on the
zirconium solids which form two preferred phases, a and y, which have the
compositions Zr(HP04)2-H20 and Zr(P04)(H2P04)-2H20, respectively. In these
layered materials, a two-dimensional metal lattice is formed and separated from an
adjacent metal lattice by the organic layer in the phosphonates or by the hydrogen
bonds from the fourth hydroxy site in the phosphates. The interlayer area in these
solids forms a possible domain for intercalation of inorganic materials such as
amines.53
i*
O o
Figure 1.8: Crystal structure of zirconium phosphate.53
The crystal structure of the Zr-phenylphosphonate solid was determined in the
1980's and found to form a structure similar to the a-phase. Subsequent studies
revealed that any alkyl or aryl group whose area was under 24 2 would form an
identical metal lattice structure while only the interlayer distance changed. In the n-


61
of the films. Aggregation is decreased or eliminated in the films of the tetra-
substituted PdP4 when transferred at very high mean molecular area MMA and at high
subphase pH. Mixtures of this amphiphile with ODPA transferred at high
temperatures (40C) and high MMA showed a similar decrease in inter-chromophore
interaction. The four long-chain phosphonic acid substituents significantly aid the
spreading of monomeric porphyrin species and the strength of the zirconium
phosphonate interaction assures their isolation in the transferred films. In similar
studies of the mono-substituted PdP 1, aggregation was observed under all of the
transfer conditions explored, indicating that none of the deposition procedures
overcome the tendency of the molecules to aggregate.
3.2. Results
3.2.1. UV-vis of Palladium Porphyrin Solutions
The palladium porphyrins show spectral responses in the UV-vis consistent
with hypso-type metallo-porphyrins. For each porphyrin, a strong Soret Band (or B
Band) is present above 400 nm and two Q Bands are centered around 550 nm.80>124
Solution studies of the porphyrins PdP4 and PdPl were performed in ethanol and
chloroform, and the absorbance dependence on concentration was investigated.
Solutions ranging from lO*11 M to 10'6 M were studied (Figure 3.3). In CHCI3, the
Soret Band was consistently at 410 to 411 nm for the porphyrin PdP4. In CHCI3,
therefore, PdP4 shows no sign of solution aggregation. For porphyrin PdPl at 10"11
M, the Soret Band absorbed at 411 nm; however, as the concentration was raised, the
Band shifted to 414 nm. Because PdPl has only one long chain substituent, the
likelihood of aggregation is increased; therefore, in CHC13, the PdPl chromophores J-
aggregate at high concentrations.76-92 Interestingly, the Soret Bands for both PdP4


8
1.1.1.4 Langmuir-Blodgett film characterization. The quality of the transferred
film is first indicated by the transfer ratio, which is a measure of the change in the area
of the monolayer versus the area of the substrate coated by the monolayer. A transfer
ratio of unity indicates that the monolayer is transferred with the same area per
molecule that it had on the water surface. This "perfect" transfer ratio assumes that the
monolayer on the water surface was stable and was not reorganizing significantly
during transfer. A consistent deviation from unity could imply a change in
organization upon transfer; however, if the transfer ratio is irregular, the transferred
film is probably poor quality.15
There are many analytical techniques used to study transferred films. Film
characteristics typically of interest are thickness, interlayer spacing, molecular
orientation and packing, film coverage, surface topology, chemical composition, and
optical and magnetic properties. The techniques used to study these parameters are
well described in the literature.20
X-ray diffraction is a reliable technique to probe interlayer spacing, and from
interlayer spacing, film thickness can be inferred. The X-rays are essentially reflected
from planes of higher electron-density. The interaction of X-rays with the crystalline
planes can be described by Braggs law (Equation 1.2):
n/l = 2c/sin? (1.2)
where n is an integer, A. is the wavelength of the radiation, d is the interlayer spacing,
and 0 is the angle of incidence and reflection of the beam.27
Ideally, there should be a significant difference between the electron density of
the head group and that of the hydrophobic region allowing X-ray diffraction peaks to


161
Figure 6.8: SA ImODPA/SA MnP4 after rinsing and after 24 hr in catalysis reaction
with excess H202.
Also, the epoxide yield with the film was now around 0.5% nearly identical to that
seen in the homogeneous and blank reactions run in vials. Interestingly, when this
reaction was run in a vial with 1 pmol of MnPO, mimicking the literature procedure,
the yield was 74%, closely resembling the yield reported with a MnTFPP Cl
catalyst.116
6.2.2.2. Oxidation with 102 times less catalyst vs. other reactants t.8 umol
FFO-, or .4 umol cvclooctene vs.l nmol MnPk Because the epoxide yield in the above
reactions may be lower than usual due to the very small amount of catalyst present
relative to reactants, an attempt was made to bring these concentrations closer to the
literature ratios of 10:1 reactant to catalyst. Additionally, this oxidant concentration
(400 pmol vs. 1 nmol catalyst) clearly causes the degradation of the porphyrin films.


99
4.11: MnP4 transferred by LB at 0.7 mN m'1 and rinsed in CH3CN: A) transferred
from a 0.5 mg mL'1 solution.
4.2.3.2. Transfer of MnP4 from a chloride ion-containing subphase. In order
to avoid intramolecular phosphonic acid-manganese binding upon LB transfer,
chloride ions were incorporated into the subphase at a 0.1 M concentration. The
porphyrin was spread and compressed to 4 mN m'1 for transfer onto a zirconated
ODPA template. In the spectrum shown in Figure 4.12, Soret Bands were observed at
461 nm and 476 nm. Clearly, there exist domains of five-coordinate MnTPP(Cl) and
six-coordinate MnTPP(Cl)(PA) structures.


156
Figure 6.6: SA ImODPA/SA MnP4 studied with PhIO for epoxidation of cyclooctene.
The CyOO yields using these mixed films were actually reduced relative to the
pure porphyrin films with PhIO. The lower yield could be due to a decreased
porphyrin concentration in the mixed films. The UV-vis spectrum of the films used
for this study demonstrated that the overall absorbance of the Soret Band prior to
catalysis was lower than that observed in the pure porphyrin film (Figure 6.6). This
result corresponded to the behavior often observed in Chapters 5 where porphyrin
substitution into a preformed capping layer resulted in a slightly lower loading than in
the pure self-assembled films.


116
which again, exist due to an irreversible binding of the phosphonic acid to the
manganese central metal under certain conditions causing the demetallation of the Mn-
porphyrin.
350 400 450 500 550
Wavelength (nm)
Figure 5.4: Solvent response of A) MnPO and B) MnP4 to ImODPA. Legends
indicate the molar ratio of MnP to ImODPA.
ImODPA was also added to a CHCI3 solution of MnP4. The spectral behavior
of this solution was more unusual. With 1 eq. of ImODPA, the red shoulder appeared


166
(39) Byrd, H.; Pike, J. K.; Talham, D. R. Syn. Met. 1995, 71, 1977-1980.
(40) Seip, C. T.; Byrd, H.; Pike, J. K.; Whipps, S.; Talham, D. R. In Physical
Supramolecular Chemistry, Echegoyen, L., Kaifer, A. E., Eds., 1996; Vol. 485.
(41) Seip, C. T.; Byrd, H.; Talham, D. R. Inorg. Chem. 1996, 35, 3479-3483.
(42) Seip, C. T.; Granroth, G. E.; Meisel, M. W.; Talham, D. R. J. Am. Chem. Soc.
1997,119, 7084-7094.
(43) Clearfield, A. Chem. Mater. 1998,10, 2801-2810.
(44) Cemto, G., Trifiro, F., Ebner, J.R., Franchetti, V.M. Chem. Rev. 1988, 88, 55.
(45) Frink, K. J.; Wang, R.-C.; Coln, J. L.; Clearfield, A. Inorganic Chemistry
1991,50, 1438-1441.
(46) Cao, G.; Mallouk, T. E. Inorganic Chemistry 1991, 30, 1434-1438.
(47) Cao, G.; Lynch, V. M.; Yacullo, L. N. Chem. Mater. 1993, 5, 1000-1006.
(48) Drumel, S., Janvier, P., Bujoli-Doeuff, M., Bujoli, B. J. Mater. Chem. 1996, 6,
1843-1847.
(49) Kaschak, D. M., Johnson, S.A., Hooks, D.E., Kim, H.-N., Ward, M.D.,
Mallouk, T.E. J. Am. Chem. Soc. 1998,120, 10887-10894.
(50) Kraus, K. A., Phillips, H.O. J. Am. Chem. Soc. 1956, 78, 644.
(51) Alberti, G. Acc. Chem. Res. 1978,11, 163.
(52) Clearfield, A. Chem. Rev. 1988, 88, 125-148.
(53) Clearfield, A. In Progress in Inorganic Chemistry, John Wiley & Sons: NY,
1998; Vol. 47.
(54) Cao, G.; Lee, H.; Lynch, V. M.; Mallouk, T. E. Solid State Ionics 1988, 26, 63-
69.
(55) Cao, G.; Lee, H.; Lynch, V. M.; Mallouk, T. E. Inorg. Chem. 1988, 27, 2781-
2785.
(56) Cunningham, D.; Hennelly, P. J. D. Inorg. Chim. Acta 1979, 37, 95-102.
(57) Zhang, Y.; Scott, K. J.; Clearfield, A. Chemistry of Materials 1993, 5, 495-
499.
(58) Cao, G.; Lynch, V. M.; Swinnea, J. S.; Mallouk, T. E. Inorganic Chemistry
1990, 29,2112-2117.


158
PhIO reaction contents were removed from the cell, it appeared that decane is retained
in the cell. The decane is even observed in the GC traces after the cell has been
thoroughly cleaned, implying that this molecule has a tendency to adsorb onto the
tubing and/or cell material and dissolves out slowly. The amount of decane seen after
the cells were cleaned is small relative to the original peak, but this may be the source
of some discrepancy observed between blanks and homogeneous reactions run in and
out of the cell.
Overall, it appears that there is an improvement observed in the catalytic
activity of the porphyrin from the homogeneous solution to that seen in the
immobilized films. These systems clearly need to be studied using an alternative
internal standard to potentially eliminate the discrepancy observed with leeching of the
decane into and then out of the flow cell.
Table 6.5: Comparison of blanks and homogeneous epoxidation yields in vials vs. in
the reaction cells.
SA MnP4 Cyclooctene oxide Turnovers
Yield
Blank in vial 1.3%-2.0%
Blank in cell 6.0%-6.5%
Homogeneous in vial 6.0%
Homogeneous in cell 9.0%-14.0%
Film in cell 20.0%-21.0%
300
450-700
1000


Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
METALLO-PORPHYRIN CONTAINING ZIRCONIUM PHOSPHONATE
THIN FILMS: STRUCTURE AND CATALYSIS
By
Christine Marie Nixon Lee
August 2000
Chairperson: Daniel R. Talham
Major Department: Chemistry
Thin films containing mono- and tetra-phosphonic acid palladium tetraphenyl
porphyrins and tetra-phosphonic acid manganese tetraphenyl porphyrins, PdPl, PdP4,
and MnP4, were prepared by both Langmuir-Blodgett (LB) and self-assembly (SA)
techniques. Within the hydrophilic regions of these films was incorporated a
zirconium phosphonate network which lent significant stability and flexibility of
preparation to these films.
In the LB films of the palladium porphyrins, it was found that the mono-
phosphonic acid porphyrins aggregated under all film preparation conditions and in
solutions at high concentrations. However, the chromophore aggregation could be
controlled in the tetra-phosphonic acid porphyrins when the films were transferred at
mean molecular areas greater or near the mean molecular area of the chromophore
itself. Self-assembling the PdP4 was another means of controlling the chromophore
xm


40
oriented parallel to the surface. In contrast, the monophosphonic acid substituted
PdPl aggregates under all of the deposition conditions studied.
Stability of the Pd-porphyrin LB and SA films was examined by exposing the
films to refluxing chloroform. UV-vis absorbance after immersion in chloroform
confirmed conclusions that in films of PdPl, many of the chromophores are not
tethered to the inorganic network and are easily removed, whereas in films of PdP4, all
molecules bind to the zirconium phosphonate extended network making these films
very resilient.
Study of the Pd-porphyrins led to significant understanding of the behavior of
tetra- and mono-phosphonic acid porphyrins in LB films. Chapter 3 describes the
results of these studies, which were the first to show incorporation of porphyrins at the
exterior of metal-lattice containing films.
Manganese tetraphenyl porphyrins are well known epoxidation
catalysts,9799116 and the incorporation of these catalysts into zirconium phosphonate
films should improve their catalytic efficiency as well as their stability and
recoverability. Films containing manganese 5,10,15,20-tetrakis(2,3,5,6-
tetrafluorophenyl-4-octadecyloxyphosphonic acid)porphyrin (MnP4) have been
prepared using the LB and SA techniques. The formation of these films involved
modifying traditional LB procedures with SA techniques, which is possible with the
use of zirconium phosphonate networks. From Langmuir monolayer and LB studies
of the pure tetraphosphonic acid porphyrin, it appears that the MnP4 amphiphiles tend
to form face-to-face aggregates, or H-aggregates, when assembled at the air-water
interface, and this aggregation is translated into the transferred films. Attenuated total
reflectance (ATR) IR, UV-vis, XPS and stability studies confirm the presence of the
porphyrin. Thorough characterization of the MnP4 containing films is described in
Chapter 4.


112
of the ImODPA made this molecule impossible to transfer as pure LB films.
However, the ImODPA could be mixed with a good film-forming molecule such as
ODPA or HDPA (hexadecylphosphonic acid), and these LB films were transferred
successfully.
The film preparation methods fall into two general categories. First, the two
components, ImODPA and MnP4, were assembled by either LB or SA in two separate
steps. Examples include mixed ImODPA/HDPA LB films onto which MnP4 was self-
assembled, ImODPA SA films followed by MnP4 SA, and MnP4 LB or SA films with
ImODPA SA in the second step. The mechanism of the second SA step is less
straightforward than the first. The phosphonic acid tethers on the second amphiphile
must either find vacant or defect sites in the zirconium network, or actually replace
already existing Zr-phosphonate bonds. Because this step is not a true self-assembly,
it will also be referred to as the substitution step. The second category of film
preparations involves the MnP4 and ImODPA being assembled in one step, either as a
mixed SA or LB transfer. All of the described methods were successful in
incorporating both components to some degree. The most facile involved SA of
ImODPA followed by substitution of MnP4.
Following the formation of the ImODPA film, MnP4 could be substituted from
CHClj, EtOH, or EtOHAvater. Immediately after substitution, some MnP4s were
physisorbed to the surface and were easily removed by rinsing in a hot solvent. The
chromophores that remained contained at least one phosphonic acid tether bound to
metal phosphonate base. Film stability was followed by UV-vis, and after the first 5
min of exposure to hot solvents, no more significant chromophore loss was observed.
One goal of this project was to understand the propensity of the imidazole
ligand to bind to the porphyrin and to determine certain characterization signatures to
confirm that this binding had taken place. That the imidazole/porphyrin binding be


9
be observed in LB films. The d-spacing, which quantifies the periodicity between
planes of high electron density, therefore, is the measure of the distance between head
groups. This technique is very sensitive to long-range periodicity, and many narrow
00/ peaks are typically indicative of a well-defined layered architecture (Figure 1.3).23
Figure 1.3 X-ray diffraction diagram.
To study the chemical make-up of the surface, attenuated total reflectance
FTIR (ATR) and X-ray photoelectron spectroscopy (XPS) are employed. ATR studies
involve transferring a film onto a crystal, such as parallelogram-shaped germanium or
silicon crystal with ends cut at 45 angles. This is an ideal method for recording the IR
spectra of films because it allows the film to be sampled many times due to the
internal reflection of the IR beam through the crystal. ATR also provides information
about the surface coverage and packing modes. Further, polarized studies using this
technique can give information about the film organization and orientation (Figure
1.4).15 Background information pertaining to films studied by ATR-IR, allows


152
From Table 6.1, it is clear that the conversion of CyO to CyOO is time
dependent. The best yields were usually achieved after 24 hr; however, the difference
between 6 hr and 24 hr was small in some cases. Although the absorbance intensity
prior to the reaction was roughly the same as in the case of the SA films, after 24 hr,
the overall absorbance intensity has decreased. This result indicates that a percentage
of the chromophores have been bleached or removed from the surface. Considering
studies done previously on the stability of the porphyrin containing zirconium
phosphonate SA and LB films after rinsing in hot solvents, the chromophores are
probably not removed but have likely been oxidized rendering them useless as
catalysts. However, the bleaching process was not complete and there were still a
number of catalytic porphyrins available on the surface.
Figure 6.4: Bleaching of MnPO in homogeneous catalysis reaction with PhlO.


46
The surface area of the 2000 trough was 343 cm2 (36.5 cm x 9.4 cm). A
platinum or filter paper Wilhelmy plate, suspended from a KSV microbalance,
measured the surface pressure. Subphases were usually pure water with a resistivity of
17-18 MQ cm_1 produced from a Bamstead NANOpure (Boston, MA) purification
system.
The films were transferred from the aqueous surface onto solid supports. Glass
microscope slides and glass coverslips were purchased from Fischer (Pittsburgh, PA)
and were used as substrates for UV-vis and catalysis studies. Single crystal silicon
wafers (10 0) were purchased from Semiconductor Processing Company (Boston,
MA), and cut using a diamond glass cutter to 25 mm x 15 mm x 0.8 mm for XPS
studies. These substrates were cleaned using piranha etch, which is 1:4 H2S04: 30%
H202, a new hydrophilic surface was prepared by the RCA procedure,117 which
involved first, heating in a 5:1:1 solution of water, 30% H202, and NH4OH, and
second, heating in a 6:1:1 solution of water, 30% H202 and HC1. Then the substrates
were sonicated for 15 minutes each in methanol, 50/50 by volume methanol/
chloroform, and chloroform. The substrates were then sonicated in a 2%
octadecyltrichlorosilane (OTS) solution in hexadecane and CHC13 for two hours.
Finally, the substrates were sonicated for 15 minutes each in CHC13, 50/50 by volume
CH3OH/ CHC13, and CHjOH.11
2.1.2. Characterization
2.1.2.1. UV-vis. Transmittance UV-visible experiments were performed on a
Cary 50 spectrophotometer by Varan with an average resolution of 2 nm. Porphyrin
solutions were studied by UV-vis in EtOH, H20, CHC13, and CH2C12 solvents. The
behavior of the porphyrin with different potential ligands was investigated by mixing
the porphyrin solution with ethylphosphonic acid, t-butyl ammonium halides (chloride


93
Figure 4.6: Solution UV-vis investigation of MnP4s sensitivity to displacement of R-
PO(OH)2 by chloride at 1 x 10'5 M (CHC13). The arrows indicate the changes in the
intensity of the peaks as the chloride concentration changes from 0.0 M to 0.1 M while
the concentration of MnP4 was constant.
4.2.2. Langmuir Monolayers
The monolayer behavior of MnP4 was studied using surface pressure (IT) vs.
Area (MMA) isotherms on water (Figure 4.7). Investigating the tilt angle of the
chromophores transferred at various surface pressures by polarized UV-vis gave some
indication of the chromophore orientation in the monolayers. The 1T-A isotherm
showed a distinct n onset at ca. 250 2 molecule'1. However, the approximate area of
the chromophore itself is ca. 200 2 molecule'1. This large onset area implied that the
alkyl chains were initially buckled so both the chromophores and the phosphonic acid
groups were sitting on the water surface. The hydrophilic nature of the porphyrin,
especially if the two axial positions are coordinated with water, makes this a viable


119
change in the ratio of Band V to Band VI is often reportedly associated with a change
in the ligand environment.7981 Unfortunately, many possible ligand changes are
present in these systems. Most likely, as the film was rinsed, the chloride ligands
could have displaced the phosphonic acid ligands. However, from the solvent studies
of the pure MnPO with ethylphosphonic acid described in Chapter 4, a decrease in
V/VI was associated with increased phosphonic acid binding. Therefore, trends in
these ratios were difficult to follow because so many scenarios were possible.
Figure 5.5: UV-vis of ODPA/Zr/HDPA, SA MnP4 film rinsed in hot CHC13.
5.3.1.2. MnP4 substituted into an ImODPA/HDPA LB film. Though HDPA
was easily transferred onto the Zr-ODPA template using the LB method, imidazole
was much more difficult to deposit in this manner. The hydrophilic nature of both the
phosphonic acid and the imidazole made this molecule unsuitable for Langmuir


67
characteristics of the liquid-condensed phase of ODPA, although features present in
the isotherms of the pure porphyrins are also present in the isotherms of the mixed
films (Figure 3.5 and 3.7).
Wavelength (nm)
Figure 3.8: Reflectance UV-vis of PdPl on water subphase.
In addition, the collapse pressure increases with the concentration of ODPA indicating
that the films become more stable as ODPA is added. However, diluting the porphyrin
film with ODPA does not appear to greatly affect the aggregation. Reflectance UV-
vis of a Langmuir monolayer of a 1:9 mixture of PdP4 with ODPA is shown in Figure
3.9. The 7.max shifts from 415.5 nm at high MMA to 420 nm as the film is
compressed, just as it does in the films of pure PdP4 (Figure 3.9). However, the
porphyrins do not appear to be aggregated in the mixed film at high MMA.


TABLE OF CONTENTS
gage
ACKNOWLEDGMENTS ii
LIST OF TABLES vii
LIST OF FIGURES viii
ABSTRACT xiii
CHAPTERS
1 INTRODUCTION 1
1.1 Ultrathin Films 1
1.1.1 Langmuir-Blodgett Films and Characterization 3
1.1.2 Self-assembled Films 15
1.2 Hybrid Organic/Inorganic Ultrathin Films Based on Layered Solids 16
1.2.1 Background 16
1.2.2 Self-assembled Films Incorporating Metal Phosphonate
Binding 19
1.2.3 Metal Phosphonate Langmuir-Blodgett Films 20
1.2.4 Dual-Function Langmuir-Blodgett Films 23
1.3 Background on Porphyrins 24
1.3.1 Optical Behavior of Porphyrins 24
1.3.2 Background on Manganese Porphyrins 33
1.3.3 Immobilization of Porphyrins 35
1.3.4 Heterocyclic Ligand Cocatalysts 36
1.4 Dissertation Overview 38
2 EXPERIMENTAL 42
2.1 Langmuir-Blodgett and Self-Assembled Film Preparation Procedure 42
2.1.1 General Langmuir-Blodgett and Self-Assembly Procedures 42
2.1.1 Characterization 46
2.2 Porphyrin Films 48
2.2.1 Palladium Porphyrin Films 48
2.2.2 Manganese Porphyrin Films 49
IV


102
Figure 4.14: SA MnP4 films with rinsing in hot CH3CN.
All of the described Band Vii intensity increases were observed after rinsing in
hot solvents. If, as was expected, the axial environment of the porphyrin was
associated with the mobility of these anions in solubilized films, the effect should be
even more pronounced while these films were in solution. To study this, MnP4 films
were self-assembled onto substrates that were cut to fit inside a cuvette filled with hot
solvent, and the UV-vis was taken immediately after the solvent was heated. The
results were, as predicted, exaggerations of what was observed when the film was
removed from the solvent. Figure 4.15 shows that after 5 min in hot solution, the ratio
V/VI was ca. 1.0, and dropped drastically up to 60 min in hot solvent as Band VI


103
increased in intensity and area. But, immediately after the film was removed from the
solvent, Band VI dropped leaving the V/VI ratio, again, greater than 1.0.
Figure 4.15: UV-vis response of a SA MnP4 film during rinsing with hot CH3CN.
Polarized UV-vis results were obtained from the self-assembled films of the
MnP4. The chromophore tilt angle was 90 at all self-assembly times. The self-
assembly of the MnP4 was facilitated by the strong binding between the zirconated
phosphonate template and the phosphonic acids on the MnP4 molecules, and the
position of the phosphonic acids on the periphery of the chromophore lends it to lie
flat in the films.
When the MnP4 was self-assembled onto a zirconated ODPA template, and
these films were then rinsed in hot CHC13 or CH3CN, the Soret Band conversion from


148
cells containing the MnP4 film. The films used in these experiments were prepared by
self-assembling a monolayer of MnP4 onto a zirconated ODPA template and rinsing
this template with hot CH2C12. The UV-vis band, Va, which has previously been
assigned to the free-base porphyrin, is clearly present in the films used for the 24 hr
and 2 hr experiments.
When these reactions were allowed to proceed over 24 hours, GC results
indicated that the average yield in the blank was ca. 1.5 %, in the homogeneous
reaction was 8.4%, and in the films, between 20% and 35%. These percent yields, as
calculated relative to the internal standard peak, were fairly consistent.
Figure 6.1: SA MnP4 film before and after 24 hr. catalysis run with 40:5:20
cyclooctene: PhIO:decane in CH2C12.
Interesting to note is the fact that, even after 24 hr in the catalysis reaction,
there does not appear to be a significant bleaching effect. The porphyrin appears to
still be present and intact in the film. What is noticeable is the fact that the Soret Band


28
However, there are also "irregular" porphyrins. Irregular porphyrins, typically
metalloporphyrins, are broken down into categories called hypso- and hyper
porphyrins. In the case of irregular porphyrins, the central metal contains partially
filled shells, which introduce a possibility of metal electrons mixing with porphyrin 71-
electrons. This mixing is caused by the possibility of metal to porphyrin back-binding
due to similar energies of the metals d-orbitals and the porphyrins 7t-orbitals. The
central metal ion can lead to significant changes in the optical and emission spectra.
The metal and its oxidation state determine which category the porphyrin's optical
behavior will fall into. Also, the release of electron density from the metal to the
porphyrin enables the metal to stay co-planar with the chromophore as the effective
size of the metal is reduced.79
Hypsoporphyrins have central metals of groups eight through eleven with
configurations dm where m = 6 9 and have filled eg(d7i) orbitals. The inclusion of
these metal ions is often associated with a bathochromic or blue shift relative to the
corresponding free base porphyrin. Common hypsoporphyrins include Ni(II), Pd(II),
and Pt(II)-porphyrins. The Ni(II) porphyrins are easily affected by basic axial ligands,
whereas Pd(II) and Pt(II) are typically four coordinate and appear insensitive to the
potential ligand environment 80>81
The second class of irregular porphyrins is called the hyperporphyrins, which
is further broken down into subclasses called p-type, d-type, and pseudonormal
hyperporphyrins. Most metallo-porphyrins classified as hyperporphyrins have central
metals with easily accessible lower oxidation states. Of these, Mn(III) and Fe(III) are
the most well studied due to their biological implications. The spectra of
hyperporphyrins exhibit the Soret and Q-Bands as before with some possible shifting.
Additional prominent absorption bands may be seen typically at higher energies
relative to the Soret Band. The hyperporphyrin spectra demonstrate the effects due to


making and teaching others to make the porphyrins and ligands on which this
dissertation is focused, Merci!
Quick notes of thanks are also due to the Butler Polymer Research
Laboratories for sharing their instrumentation and to Eric Lambers and the Major
Analytical Instrumentation Center for allowing me to use the XPS. Also, thanks to
Joe and Raymond in the chemistry department machine shop for working with me on
designing and building the catalysis flow cells.
Without many wonderful friends, my time at University of Florida would have
been much less enjoyable. So, I thank Louann Troutman, Tracey Hawkins, Dean and
Annie Welsh, Denise Main, and Debby Tindall, and of course, Jen Batten and Leroy
Kloeppner (and Alex) the greatest of friends. I owe Jen and Leroy special thanks,
not only for their efforts in editing this dissertation, but also for their support and love
along the way.
And lastly, my family. All the gratitude in the world goes to my mom and dad,
Pat and Ron, and to my brothers Joe and John and my soon-to-be sister, Jullia. And to
my grandmothers, Evelyn Nixon and Margaret Loeber, and in memory of my
Grandpas Bill and Lee. I have been truly blessed. Thanks, too, to my new family,
George and Agnes, Brian and Greg Lee who are the best second family I could
imagine.
To my husband, Larry, my best friend and biggest fan, I owe more thanks than
can be expressed.
in


132
many complications with the films prepared in this way. First, the imidazole will most
likely want to bind to the exposed surface of the porphyrin first; however, the
phosphonic acid will be trying to bury into the film to find the zirconium network.
Further, it is very difficult to confirm the presence of the imidazole in these films by
any means. Therefore, this method was not rigorously pursued.
Wavelength (nm)
Figure 5.15: ImODPA substituted into a MnP4 LB film transferred at 10 mN m'1.
5.3.4.2. LB transfer of mixed MnP4/ImODPA film at high pH. For
comparison, a LB film was prepared from a spreading solution containing MnP4 and
ImODPA in a 1 to 3 ratio. Ideally, a monolayer richer in ImODPA would have been
used, but again, this is a poor amphiphile for LB films, and so this was impossible.
These films were transferred at a variety of pressures and pHs. In a film transferred
before the onset of the isotherm at a pH of 11.3 (Figure 5.16), the Soret Band after was
at 459 nm. When the film was transferred at a MMA associated with little


124
The ratio of ImODPA to HDPA has been varied, and MnPO films were still
successfully formed. Further, using an ImODPA/ODPA mixture instead of
ImODPA/HDPA also worked to prepare the MnPO films. The 25% ImODPA films
were studied primarily because of the balance of high imidazole loading and stable
film behavior. HDPA was the primary diluent used because its chain length was
appropriate to form a film with the imidazole group fully exposed and available for
binding.
Figure 5.9: MnPO attached to a 25% ImODPA/HDPA LB film and rinsed in hot
CHClj.
5.3.2, Mn-porphvrins substituted into self-assembled films of ImODPA
5.3.2.1. UV-vis response of MnP4 film to f-butyl amine and CHCU rinsing.
MnP4 was successfully substituted into a SA layer of ImODPA. After substitution,
the films were rinsed with a solution of t-butyl amine (7-BuNH2) to deprotonate the
imidazole and facilitate its binding to the porphyrin. The base /-BuNH2 was chosen


on-gold surface.30 XPS, therefore, clearly demonstrated the presence of both the
porphyrin and the imidazole in the films.
136
Figure 5.18: XPS multiplex scan of Nls region of ImODPA/MnP4 film self-
assembled out of 70/30 CH2C12 solution. The dashed lines represent the Gaussian
peak fits.
Figure 5.19: XPS multiplex scan of ImODPA/MnP4 film self-assembled from a 70/30
mixture in EtOH/H20. The dashed and dotted lines represent gaussian peak fits.




120
monolayer formation. Therefore, the imidazole was diluted with HDPA or ODPA to
avoid this problem. After the LB transfer of the ImODPA:HDPA mixtures, the MnP4
was substituted into this layer. When films containing solutions ranging from 10% to
75% ImODPA in HDPA were prepared and the MnP4 was substituted into these films,
a pattern was observed (Figure 5.6). In the films of 10% ImODPA, SA MnP4, the
ratio of V/Va was clearly less than 1.0. This ratio increased with an increased
concentration of ImODPA. Band Va, associated with the free-base porphyrin, drops in
intensity with the addition of an imidazole ligand to compete with the phosphonic
acid, as was seen in solution studies with MnP4 and ImH (Figure 5.3B). The
presence of free-base porphyrin is possibly due to the irreversible binding of
phosphonic acid to manganese that then pulls the manganese out of the center of the
chromophore. Therefore, if the imidazole prevents the phosphonic acid from binding,
it may preserve the integrity of the metallo-porphyrin.
Likewise, though less dramatic, the ratio of V/VI also appeared to increase
with added ImODPA. Unfortunately, the ratio of V/VI in these films was not always
reproducible or controllable, and this ratio fluctuation was observed in films when
imidazole was absent. These inconsistencies could be due to the inability to
completely direct the axial binding of the metallo-porphyrins.
The Soret Band in Figure 5.6 demonstrates splitting after rinsing in hot CHC13.
The blue side of the peak occurs at 462 nm, which is slightly red shifted from the peak
previously attributed to imidazole binding. However, as the percentage of imidazole
increases, Band Vi appears to shift slightly to the blue. Also, the occurrence of the
second, red band at 477 nm indicates the presence of halide axial ligands assigned to
MnTPP(Cl). Due to the steric constraints from the film environment, it is unlikely that
these porphyrins would form bis-imidazole complexes [MnTPP(Im)2]. Therefore, this


137
5.3.5.3. ATR-IR characterization of the films containing substituted MnP4 on
a self-assembled ImODPA layer. An ODPA monolayer transferred by the LB
technique onto a Zr-ODPA template leads to alkyl peaks at 2918 cm-1 and 2850 cm'1
corresponding to the va(CH2) and vs(CH2) stretches, respectively. For alkyl chains in
a majority tram-configuration with crystalline order, the va(CH2) peak usually falls
between 2918 cnr1 and 2920 cm'1. A shift to higher energies indicates the
introduction of disorganization within the hydrophobic region of the film. In addition,
the full width at half maximum (FWHM) of the va(CH2) peak can be a measure of the
packing and conformational order within the alkyl region. An organized, close-packed
film has a FWHM of approximately 17 cm'1, which can stretch to 35 cm'1 upon
disorganization of the film.
In films formed by both the LB and SA of ODPA from a 9/1 EtOH/H20
solution onto a zirconated ODPA template, the va(CH2) stretch comes at 2918 cm'1
and the vs(CH2) is at 2850 cm'1. Therefore, these films are mostly trans and close-
packed. In addition, the absorbance intensity of the va(CH2) peak in the capping layer
is between 0.012 and 0.015 au. An alkyl absorbance intensity of this magnitude is
therefore associated with the formation of a complete, organized monolayer of an
octadecyl amphiphile.
In order to further confirm the presence of imidazole in the films formed by the
SA of ImODPA onto a zirconated ODPA template, the va(CH2) and vs(CH2) peaks
were monitored and compared to the ATR-IR results obtained from the ODPA
monolayer. The ATR-IR spectra of the ImODPA films were referenced to the
zirconated ODPA template; therefore, what was plotted were the results from just the
ImODPA capping layer. When the Zr-ODPA template had soaked in a 9/1 EtOH/H20


95
region b, the Soret Band shifted to and remained at 453 nm. The blue shift
corroborates the formation of face-to-face dimers. The mean molecular area of this
spectral shift indicated that dimers began forming even before all of the chromophores
were pushed off of the water surface.
Wavelength (nm)
Figure 4.8: Reflectance UV-vis of MnP4 on water subphase.
4.2.3. Langmuir-Blodgett Films of pure MnP4
4.2.3.1. Deposition of MnP4 from a pure water subphase. Using the LB
technique, the MnP4 monolayers were transferred at various points along the isotherm.
The transmittance UV-vis spectra of these films showed that the blue shift in the Xmax
followed the shift observed in the reflectance UV-vis experiments on the water surface
(Figure 4.9). Films transferred around 5 mN m'1 had a ^max at 462 nm, while films
transferred at pressures higher than 10 mN m*1 were blue shifted to 456 nm. The Soret
Band blue shift suggested that the chromophores were interacting as H-type


73
190 2 molecule'1 and 300 2 molecule-1 where the tilt angle, 0, with respect to the
surface normal is observed to be 90. Interestingly, the porphyrins also appear to lie
parallel to the surface in the films transferred at 130 2 molecule'1 where 0 is also
measured as approximately 90. This result implies that in films transferred at areas
smaller than the MMA of the flat porphyrin macrocycle, the molecules overlap,
stacking in bilayers or multilayers but with very little change in the tilt angle. There is
a larger uncertainty, possibly 10, in the measurement as the tilt angles near 90 ;26
however, these results confirm that the chromophores are lying approximately flat in
all of the films in this study.
Multilayers of the alternating ODPA/Zr/PdP4 films can be deposited and X-ray
diffraction confirms the layered nature of the films. Two or three orders of the (00/)
Bragg peaks can be observed in each case. Films transferred at 190 2 molecule'1
have a bilayer thickness of 42 , which is smaller than the 48 thickness seen in pure
ODPA/Zr/ODPA bilayers,28 suggesting that the 18-carbon tethers of PdP4 are not
fully extended in the alternating films. For the film transferred at 130 2 molecule-1,
the bilayer thickness increases to 47 as the tetrasubstituted chromophores begin to
overlap.
Symmetric bilayers of PdP4/Zr/PdP4 fabricated according to Figure 2.2, were
also studied. Porphyrin PdP4 could be transferred on the down stroke onto a
hydrophobic substrate under a variety of conditions. After zirconation, deposition of a
capping layer of PdP4 results in a symmetric bilayer. The Soret Band is very similar
to that from alternating films deposited at the same area per molecule, and polarized
UV-vis indicates the porphyrins are also lying parallel to the surface. However, the
layers are poorly organized, as (00/) Bragg peaks could not be seen in diffraction from


135
The layer of pure imidazole was scanned by the multiplexing technique over the
nitrogen peak (Nls), between 410 and 390 eV. The nitrogen peak, which could only be
due to the presence of imidazole, was clearly a single Gaussian peak centered at 401.0
eV with a FWHM of 2 eV (Figure 5.17A).
When a capping layer of pure MnP4 was self-assembled onto the zirconated
ODPA template, a nitrogen peak was also seen (Figure 5.17B). However, in these
films, the nitrogen peak was broadened to 3 eV and shifted to 399.0 eV. The nitrogen
atoms of the imidazole and the porphyrin are in two different environments, and a
small change in their binding energies would be expected. Therefore, in the mixed
film, two peaks should be present in the N,s region, one representing the imidazole and
one representing the porphyrin.
5.3.5.2. XPS results from mixed self-assembled films. A film SA from a
70/30 mixture of ImODPA and MnP4 in CH2C12 was studied by XPS to determine if
two nitrogen environments could be detected. There was a strong peak at about 402.0
eV and a distinct shoulder or second peak of weaker intensity at 399.0 eV indicating
the presence of both nitrogen environments, and hence of both the imidazole and
porphyrin within the films (Figure 5.18). Alternatively, a mixture of the porphyrin and
imidazole in a similar ratio was self-assembled from 9/1 EtOH/H20. The nitrogen
region of these self-assembled films showed two peaks, the first centered at 402.0 eV
and the second, a broader peak of approximately equivalent intensity centered at ca.
400.0 eV (Figure 5.19). These peaks align reasonably well with those of the XPS
studies of the pure imidazole (401.0 eV) and porphyrin (399.0 eV).
Again, these results indicate the presence of both the imidazole and the
porphyrin in these self-assembled films. Similar results were observed by Offord et al.
in films of ruthenium or osmium metallo-porphyrins that were adhered to a SA thiol-


146
hydrophobic and hydrophilic regions were defined in the molecule and this amphiphile
formed monolayers on the water surface. These monolayers could be transferred onto
hydrophobic substrates placing the chromophore on the exposed surface. The
immobilization of these porphyrins saw a doubling of the epoxide yield as compared
to the same catalyst to reactant ratios in solution with PhIO as the oxidant.
Unfortunately, the transferred monolayer by itself was not stable and was removed
almost instantly from the surface in room temperature CH3CN. Abatti et al. used a
poly-vinylalcohol film to stabilize the porphyrin film for up to 4 hr.88
As an alternative to the homogeneous reactions and coated LB films using
porphyrins as catalysts, our work focused on immobilizing active porphyrins in
independently stable film structures. As mentioned in Chapters 4 and 5, the process
involved incorporating manganese(III) 5, 10, 15, 20-tetrakis(tetrafluorophenyl-4-
octadecyloxyphosphonic acid)porphyrin (MnP4), with and without imidazole
octadecylphosphonic acid (ImODPA), into zirconium phosphonate LB and SA films.
The film structures were stable in hot CH2C12 over 60 min and were expected to be
stable in the catalysis reactions.
The flow cells described and illustrated in Chapter 2 were employed to run
reactions using the porphyrin containing films with or without imidazole. The
different reaction mixtures were prepared and the blank and homogeneous solutions
were separated into different vials, where they were stirred for a given length of time.
The blank solution was pumped through a cell containing the film of interest for the
same amount of time. In most cases, the reactions were run for 2, 6, or 24 hr.
Because the extent of the reaction would be measured by GC, the first step in
this study involved determining the GC sensitivity factors for the cyclooctene and
cyclooctene oxide. A decane standard was used in PhIO reactions, and an o-


71
Table 3.1: UV-vis data from symmetric and alternating films of PdP4. A.max is given
for monolayers, and interlayer thickness is given for multilayers of films transferred
under a variety of transfer conditions.
Film
Transfer
Area
(2 mol.'1)*
riof
Transfer
(mN/m)
pH***
Temp
(C)
^max
(nm)
thickness
(A)
OPA/Zr/PdP4
300
5.5
23-25
416
OPA/Zr/ PdP4
190
4
5.5
23-25
418
42
OPA/Zr/ PdP4
180
5
5.5
23-25
418

OPA/Zr/ PdP4
130
15
5.5
23-25
420

OPA/Zr/ PdP4
100
25
5.5
23-25
420

OPA/Zr/ PdP4
90
35
5.5
23-25
420

OPA/Zr/10% PdP4
37
5
5.5
23-25
415

OPA/Zr/10% PdP4
33
15
5.5
23-25
418
47
OPA/Zr/25% PdP4
50
15
5.5
23-25
420

OPA/Zr/50% PdP4
74
15
5.5
23-25
420

OPA/Zr/ PdP4
300

9.4
23-25
416
OPA/Zr/ PdP4
190
4
9.4
23-25
416

OPA/Zr/ PdP4
300

11.1
23-25
414

OPA/Zr/ PdP4
85
15
5.5
40
419

OPA/Zr/ PdP4
160
4
5.5
40
417

OPA/Zr/25% PdP4
50
15
5.5
40
415

OPA/Zr/25% PdP4
60
4
5.5
40
415

OPA/Zr/10% PdP4
35
15
5.5
40
415
OPA/Zr/10% PdP4
50
4
5.5
40
415

PdP4/Zr/ PdP4
190
4
5.5
23-25
416

PdP4/Zr/ PdP4
130
15
5.5
23-25
418

10% PdP4/Zr/ 10%
37
5
5.5
23-25
418
47
PdP4
* Area of the chromophore and diluent as determined from Figure 3.5 (isotherms)
** Corresponding pressure from Figure 3.5 (isotherm)
*** pH of nano-pure water from filtration system is about 5.5


27
model (Figure 1.14), which combines the Hckel-MO theory with the free-electron
model. In this model, Gouterman describes four orbitals, two LUMOs, c,(eg) and c2
(eg) each with five nodes, which are degenerate in energy, and two HOMOs, b,(a2u)
and b2(alu), each with four nodes, which are not degenerate. According to the four
orbital model, the Soret Band corresponds to the transition from the lower energy alu
orbital to the eg orbital, giving a higher energy transition. The Q-Bands arise from the
transition from the a2u orbital, which is higher in energy giving a lower energy
transition.2580
Figure 1.14: Goutermans four-orbital model.


162
Figure 6.9: SA ImODPA/SA MnP4 film with catalysis using 8 pmol cyclooctene to
0.2 pmol H202.
The solutions were, therefore, diluted 100-fold and similar reactions were
investigated. The new reaction molar ratio was 8 pmol cyclooctene to 0.2 pmol H202
to 1 nmol of catalyst. The concentration of catalyst in the homogeneous case was set
by the concentration in the films, which could not be increased. Unfortunately, even
with excess substrate to protect the porphyrin structure, more serious catalyst
bleaching was observed in these films than in those with PhIO (Figure 6.9). In
addition, the epoxide yield with the immobilized catalyst under these conditions was
similar to or less than that observed in the homogeneous case. The reasons behind
these results are not clear.


90
studying solutions of MnPO (1 x 10'7 M in CHC13) with ethylphosphonic acid at high
concentrations. In pure MnPO, the Xmax was observed at 475 477 nm; however, when
1 x 10-4 M ethylphosphonic acid was added, a distinct blue shoulder became visible.
At ethylphosphonic acid concentrations above 3 x 1 O'4 M (over 1000 times the
porphyrin concentration) the dominant peak was the peak at 460 nm (Figure 4.5).
Further, upon addition of phosphonic acid to MnPO solutions in CHC13, an obvious
peak emerged at 418 nm. Band Va was absent in the pure MnPO solutions, hence, this
peak was probably related to phosphonic acid binding.
i i | 1 1
400 450 500
Wavelength (nm)
Figure 4.5: MnPO in CHC13 (1 x 107 M) with ethylphosphonic acid: a) pure MnPO, b)
1 x 10'4 M ethylphosphonic acid, c) 2 x 10'4 M ethylphosphonic acid, d) 3 x 10-4 M
ethylphosphonic acid, e) pure MnP4.
The peak at 418 nm could represent many different states of the porphyrin. It
could be due to the oxidation of the central metal, to a spin state conversion, or even to


96
aggregates. The chromophore interactions observed on the water surface were similar
to those observed in the deposited films; however, the at ca. 460 nm also implied
that the chromophores were intramolecularly ligating phosphonic acids.
Figure 4.9: UV-vis of MnP4 capping layers transferred onto ODPA/Zr at different
surface pressures.
The polarized UV-vis spectra were studied to better understand the orientation
of the chromophores within the monolayer. In the case of a high-spin, 6-coordinate
Mn(III)TPP, the metal typically lies within the porphyrin macromolecular plane.127
Therefore, the tilt angle of the chromophore with respect to the surface can be
determined from polarized UV-vis as described in Chapter 2 2526135 When the
monolayer was transferred in region 'a' of Figure 4.7, the tilt angle was determined to
be ca. 90. Within the plateau region of the II-A isotherm, the tilt angle immediately
after transfer was as low as 60, but within minutes, the chromophore relaxed back to a


peak splitting has been assigned to the formation of asymmetric axially bound
porphyrins coexisting with domains of MnTPP(Cl).
121
Figure 5.6: MnP4 substituted onto ImODPA:HDPA LB films after CHC13 rinsing.
Rinsing in hot CHC13 successfully eliminated any physisorbed chromophores.
However, hot CHC13 had a tendency to also cause a change in the ligand environment.
Therefore, room temperature CHC13 was examined in order to eliminate the
physisorbed chromophores. After rinsing a 25% ImODPA/HDPA LB film, MnP4 SA
film in room temperature CHC13, the UV-vis showed behavior different compared to
hot CHC13. The absorbance intensity of the Soret Band decreased along with a shift
from 456 nm to 458 nm (Figure 5.7).


12
spectrum. These two peaks were associated with the different nitrogen environments
in the imidazole and porphyrin, clearly indicating that both species were present in the
mixed film.30
The intensities of the XPS peaks can be used to determine the relative ratios of
the elements present, and can indicate the type of crystalline lattice formed. However,
the intensities of the XPS peaks are sensitive to many parameters such as the elements
electron escape depth, which can complicate the determination of the elemental ratios.
In a given sample, the observed relative peak intensities are compared to a calculated
value based on Equation 1.4:
L =
/;Zexp
di
eA{sm0)
7iZexp
~dm
+/;lexP
d
m
+ ...
eA{sind)
fi(sin0)
(1.4)
where IA is the relative intensity of element A, IA is the atomic sensitivity factor, dm is
the overlayer thickness, 0 is the incident angle of the X-ray beam, and A.e is the
inelastic mean free path. The inelastic mean free path represents the distance over
which 60% of the electrons can travel before inter-electron collisions lead to a loss of
energy31 and is defined by:32
=10[49/(^n 2) + 0.11(£Wn)05] () (1.5)
UV-vis spectroscopy reveals a films optical behavior. Typically, films are
transferred onto glass or quartz substrates and transmittance studies are performed.


LIST OF TABLES
Table page
3.1 UV-vis data from symmetric and alternating films of PdP4. A.max is given for
monolayers, and interlayer thickness is given for multilayers of films
transferred under a variety of transfer conditions 71
3.2 UV-vis data from symmetric and alternating films of PdPl. X.max is given for
monolayers, and interlayer thickness is given for multilayers of films
transferred under a variety of transfer conditions 77
6.1 Time dependence of epoxidation of cyclooctene using 40 (amol cyclooctene
and 5 pmol PhIO in lmL of solution. To the homogeneous reaction was
added lnmol ofMnPO 151
6.2 Conversion of cyclooctene to cycloctene oxide with 40 pmol cyclooctene
and 5 pmol PhIO in lmL of solution using MnP4 LB film 154
6.3 Conversion of cyclooctene to cyclooctene oxide with varying cyclooctene
to PhIO ratios in lmL of solution using MnP4 SA films over 24 hr 155
6.4 Conversion of cyclooctene to cyclooctene oxide with 40 pmol cyclooctene
and 5 pmol PhIO in lmL of solution and in films containing imidazole 157
6.5 Comparison of blanks and homogeneous epoxidation yields in vials vs. in
the reaction cells 158
6.6 Conversion of cyclooctene to cyclooctene oxide with 400 pmol cyclooctene
and 80 pmol H2O2 in lmL of solution using imidazole and porphyrin 161
vii


153
Figure 6.5: MnP4 LB film before and after 24 hr catalysis reaction.
6.2.1.2. Oxidation yield dependence on film preparation method. The above
described catalysis results were observed using MnP4 SA films. Alternatively, pure
LB films of MnP4 were also used in the reaction cells. A MnP4 film was transferred
by the LB technique at 20 mN m'1 where the density of chromophores was high and
aggregation was observed. The film was rinsed to remove any possibly physisorbed
chromophores present due to the compressed nature of the film. These films were then
used in the reaction flow cells over 24 hr with a 40:5:20 ratio of CyO to PhIO to
decane. The corresponding blank and homogeneous reactions gave yields of, again,
around 4% and 10% respectively; however, the yields with the films were around
15%, which is slightly lower than that seen in the case of the self-assembled porphyrin