Citation
Synthesis of variable bandgap conjugated polyelectrolytes via metal catalyzed cross-coupling reactions

Material Information

Title:
Synthesis of variable bandgap conjugated polyelectrolytes via metal catalyzed cross-coupling reactions
Creator:
Ramey, Michael Brian, 1973-
Publication Date:
Language:
English
Physical Description:
xii, 140 leaves : ill. ; 29 cm.

Subjects

Subjects / Keywords:
Amines ( jstor )
Catalysts ( jstor )
Fixed assets ( jstor )
Molecular weight ( jstor )
Monomers ( jstor )
Polymerization ( jstor )
Polymers ( jstor )
Reagents ( jstor )
Solubility ( jstor )
Solvents ( jstor )
Chemistry thesis, Ph. D ( lcsh )
Dissertations, Academic -- Chemistry -- UF ( lcsh )
Polyelectrolytes ( lcsh )
Polymers -- Synthesis ( lcsh )
Genre:
bibliography ( marcgt )
theses ( marcgt )
non-fiction ( marcgt )

Notes

Thesis:
Thesis (Ph. D.)--University of Florida, 2001.
Bibliography:
Includes bibliographical references (leaves 132-139).
General Note:
Printout.
General Note:
Vita.
Statement of Responsibility:
by Michael Brian Ramey.

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:
027013218 ( ALEPH )
47288961 ( OCLC )

Downloads

This item has the following downloads:


Full Text











SYNTHESIS OF VARIABLE BANDGAP CONJUGATED POLYELECTROLYTES
VIA METAL CATALYZED CROSS-COUPLING REACTIONS




















By

MICHAEL BRIAN RAMEY


A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF 4WE JN.VESITY OF FLORIDA IN PARTIAL FULFILLMENT
.OP TE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY

U .' NIVEiRS IT OF FLORIDA

*ii : : *. 2" ... .. .:'0


. ... ..

E : II" "i :E .
ii~ i:: ';;...; : i ..:i ...i ." .;..,, ;, i :


- H


: "' ..
. ** :.:


.>: J .











































This dissertation is dedicated to James B. and Jewell Q. Ramey, and Ralph and Georgia

Quails whose lifelong work, encouragement, and love have made the construction of this

dissertation possible.


;,u~bl i ;i;
i:....

I
":"


x: : ..

-I ": .... .. ".


S""'. *. .... : ".: "I .'.
..*:y.. .. :; "*,.;:,..-./.".










ACKNOWLEDGMENTS

The greatest acknowledgment goes to my Lord and Savior, Jesus Christ, whose

loving sacrifice wipes clean the imperfections of us all. My wife, Jennifer Ramey, has

walked hand in hand with me throughout my growth as a Christian and scientist and

without her support and love my life would not be complete. Family members mentioned

in the dedication essentially gave up a large portion of their lives in order to make mine a

success and that debt can never be repaid. The investment in my life was paid with the

sweat of their brow and with intellectual and emotional guidance. Now that I am

expecting the arrival of my first child in September 2001, I can only hope to reflect the

same attitude to my son or daughter.

I would also like to thank those around me in the professional arena. Dr. John

Reynolds has helped guide me through the process of becoming a Ph.D. scientist and has

set an excellent example of the life of a Christian man. Dr. Kenneth Wagener has almost

been like a second research advisor to me as he is available and helpful for all students

who come to him in search of advice on research, professionalism, or life. The students,

post-docs, and visiting scientists make the George and Josephine Polymer Research

Laboratory an outstanding environment in which to work. Special thanks go out to my

closest friends on the polymer floor: Jason Smith and Cameron Church who have had the

pleasure of jumping through the same hoops and sharing the same experiences as

members of the same entering graduate class; Dean Welsh who is a fellow NASCAR









fan, workout partner, and scientific consultant; and C.J. Dubois who is one entertaining


Cajun, but respectful and competent lab co-worker.


.1t.
..... ... ..
"' '.'. ":.. "'i:.." :,,::: : i:,-** :! "'


: ; : ... .. i
i .: .:; ;L .. .. : ; :














TABLE OF CONTENTS

page

ACKNOW LEDGMENTS ................................................................................................... iii

LIST OF TABLES .............................................. ........................................................ vii

LIST OF FIGURES......................................................................................................... viii

ABSTRACT...................................................................................................................... xi

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

The Origination of Polymer Chemistry......................................... ............................... 1
Background and Theory of Conjugated Polymers .......................................................... 2
Bandgap: From Dienes to Extended Conjugation Systems ....................................... 3
Luminescence: Photo- and Electro- ............................................ ................................ 8
Conjugated Polymers for Electroactive Applications............................................ 11
Palladium(0) Coupling Reactions ................................................................................. 13
General Catalytic Cycles and M echanism ........................................ .......... ........... ... 14
Conjugated Polyelectrolytes............................................. ......................................... 17
Scope of the Dissertation......................................................................................... 18

CATIONIC POLY(p-PHENYLENE)'S ......................................................................... 20

Introduction ............................................................................................................. 20
Early Synthetic Attempts .................................................................................... 20
Suzuki Couplings ................................................................................................ 22
Results and Discussion............................................................................................ 25
M onomer and M odel Compound Syntheses................................................... 25
Neutral Polymer Syntheses ................................................................................. 30
Polymer Quaternization....................................................................................... 39
Physical Properties of PPP Type Polymers............................................................... 41
Conclusions .......................................................................................................... 44

CATIONIC POLY(p-PHENYLENE-co-THIOPHENE)'s .............................................. 47

Introduction ............................................................................................................. 47
Early Synthetic Attempts .................................................................................... 48
Optimization of the Stille Coupling Polymerization................................. .......... ... 50
Results and Discussion............................................................................................ 54






Monomer Syntheses and Suzuki Coupling Test Reactions................................... 54
Neutral Polym er Syntheses ................................................................................. 59
Polym er Quaternization....................................................................................... 65
Physical Properties of PPT Type Polym ers............................................................ 66
Conclusions ....... .................................................................................................. 69

CATIONIC POLY(p-PHENYLENE-ETHYNYLENE)'s........................................... 71

Introduction ............................................................................................................. 71
Early Synthetic Attem pts ............................................................. .....................71
Palladium (0) Coupling Reactions ............................................................................ 72
Dialkoxy-Poly(p-phenyleneethynylene)'s ........................................ ........... ............. 75
Results and Discussion.................................................................................................. 78
M onomer Syntheses ............................................................................................ 78
Neutral Polym er Syntheses ....................................................................................... 87
Polymer Quaternization......................................................................................... 94
Physical Properties of PPE Type Polym ers................................... .............. ............ 95
Conclusions ......... ....................................................................................... ........... 99

CONCLUSIONS ....................................................................................................... 101

EXPERIM ENTAL .......................................................................................................... 107

Chapter 2 ............................................................................................................... 108
Chapter 3 ............................................................................................................... 116
Chapter 4 ............................................................................................................... 122

REFERENCES.......................................................................................................... 132

BIOGRAPHICAL SKETCH .......................................................................................... 140




*-.<


1.*


vi


3..
*h ":, 'p. I J .
. ;; ii; f.,



.:." .. p o .,r
S .* ; :" : ".:*E .. : .. .


1.











LIST OF TABLES


Table Page

1-1. Brief Summary of Emission Wavelength for Differing Conjugated Polymer
Structures.................................................................................................... 12

2-1. Catalyst effect on the molecular weight properties of PPP-NEt2 polymers................ 36

2-2. Elemental Analysis results for PPP monomers and polymers.................................. 37

2-3. Effect of DBNEt or DINEt on the molecular weight of PPP-NEt2 polymers ............ 38

3-1. Structures of the organohalides and triflates for the Stille reactions .......................... 51

3-2. Structures of the organotin monomers for the Stille reactions. .................................. 51

3-3. GC/MS results of Suzuki coupling of 2,5-thiophene diboronate ester and 4-
brom otoluene................................................................................................. 58

3-4. Gel permeation chromatography results for Stille coupling of PPT-NEt2.................... 61

3-5. Elemental Analysis results for PPT monomers and polymers.................................... 62

3-6. Summary of optical data for PPT-NEt type polymers............................................. 68

4-1. Elemental analysis results for PPE monomers and polymers..................................... 81

4-2. Summary of optical data for PPE-OC9(20) type polymers........................................ 97











LIST OF FIGURES


Figure Page

1-1. Structures of poly(p-phenyleneterephthalamide) (1), poly(benzobisthiazole) (2), and
poly(p-phenylene) (3).......................................... ................ .......................... 3

1-2. Application of Frost's circle to illustrate the energies of molecular orbitals within
cyclic system s..................................................... ............................................. 5

1-3. Band structure and density of states (DOS) diagram of a simple one dimensional
metal (polyacetylene) prior to and after a Peierls distortion........................... 7

1-4. Geometrical relaxation of a PPV chain in response to photo- or electo- excitation..... 10

1-5. Polaron, bipolaron, and singlet exciton energy levels in a non-degenerate ground-
state polym er. ...................... ............ ............................................................ 10

1-6. Electronic transitions in a conjugated polymer (i.e. PPV) showing both singlet and
triplet states. ................................................................................................... 11

1-7. General catalytic cycle for Pd(0) cross coupling reactions......................................... 15

2-1. Synthetic methods to poly(p-phenylene) ............................................................. 22

2-2. Suzuki coupling approaches to substituted poly(p-phenylene). %............................... 23

2-3. Anionic poly(p-phenylene)'s reported in the literature....... ............................ 24

2-4. Cationic poly(p-phenylene)'s reported in the literature (R = hexyl).;:.........:. ......... 25

2-5. Conversion of 1,4-dimethoxybenzene to 2,5-diiodohydroquinone. ......................... 26

2-6. Bromination of hydroquinone in the 2,5 positions ................................ ....... 27

2-7. Williamson etherification of DIHQ or DBHQ. ......................................... ........... 28

2-8. Synthesis of di-boronic phenylene reagents for use in Suzuki couplingS.:... ....- ........ 29

2-9. Synthesis of neutral and cationic PPP model compounds. .:: ........:.... ......30


S" ." .4. "": .
., ......,, f.. <.i ; :*! :- :::i: :~.. ... : ,, W f : : :,






2-10. Suzuki polymerizations for neutral alkoxy-amine containing PPP's ..................... 31

2-11. Cl-Pd-Cl bond angle for PdCl2(dppe), PdCl2(dppp), and PdCl2(dppf) catalysts........ 34

2-12. Gel permeation chromatogram for PPP-NEt2(dppf)[12].................... ........... ... 36

2-13. Envisioned boronic reagents for a more substituted PPP-NEt2 polymer................ 38

2-14. Pd catalyzed coupling to diboronic reagents for Suzuki couplings........................ 38

2-15. Q uaternization of PPP-NEt2.......................................... ........................................... 40

2-16. UV-Vis / Emission behavior of neutral and water soluble PPP-NEt.......................... 43

2-17. Photoluminescent spectrum of PPP-NEt2[12] in THF with normalized and linear
em mission scale................................................................................................ 44

2-18. TGA thermograms for neutral and water soluble PPP-NEt under N2......................45

3-1. Literature examples of phenylene-co-thiophene type polymers................................. 49

3-2. General scheme for the Stille polymerization....................................................... 49

3-3. Representative polymer repeat units of Stille polymerizations ................................ 52

3-4. Synthesis of 2,5-bis(trimethylstannyl)thiophene ..................................................... 55

3-5. Synthesis of 2,5-thiophene diboronate ester ............................................................ 56

3-6. Test coupling reaction of 2,5-thiophene diboronate ester and 4-bromotoluene.......... 57

3-7. Stille coupling polymerization scheme for PPT-NEt2................................................ 60

3-8. 'H and L"C NMR spectra of PPT-NEt2[28]............................................... .......... .. 63

3-9. Synthesis of PPT-NEt2[29] via Suzuki coupling polymerization............................. 64

3-10. Quaternization of PPT-NEt2 to form PPT-NEt3+ .................................... ........ .. 66

3-11. Normalized UV-Vis absorption and solution photoluminescence for PPT-NEt type
polym ers. ........................................................................................................ 67

3-12. TGA thermograms for neutral and water soluble PPT-NEt under N2...................... 69

4-1. Early synthetic methodologies toward poly(p-phenyleneethynylene)'s [PPE]............ 72

4-2. General reaction scheme for the Heck-Cassar-Sonogashira-Hagihara reaction........... 73

4-3. Activation of Pd(II) compound to active Pd(0) catalyst................................... 74



S .ix






4-4. Synthesis of dialkoxy poly(p-phenyleneethynylene)'s via the Sonogashira reaction.. 75

4-5. Representative structures of synthetic modifications to poly(p-
phenyleneethynylene)'s.................................................................................. 77

4-6. Williamson etherification to synthesize various 1,4-dialkoxyphenylene's. ................78

4-7. lodination of various 1,4-dialkoxybenzene's............................................................. 79

4-8. Synthesis of various 1,4-diethynylphenylene monomers ........................................... 80

4-9. Synthesis of 2,5-bis(6-bromohexyl)-1,4-diiodobenzene............................................ 83

4-10. Gas chromatography analysis of purification of 6-bromohexylmethylether (43) by
vacuum distillation using (a) simple vigreux column and (b) spinning band
column n........................................................................................................... 85

4-11. Rehahn's route to cationic PPP's........................................................................... 86

4-12. Williamson etherification to "protect" bromo endgroups........................... ....... .. 86

4-13. Envisioned application of Rehahn's strategy to PPE's.............................................. 86

4-14. General synthesis for alkoxy-amine containing PPE's.............................................. 87

4-15. 'H and '3C NMR of PPE-NEtz/OC9(20)[54] in CDC3 ............................................ 92

4-16. Expansion of the aromatic region of the 'H NMR of PPE-NEt2/OC9(20)[54] in
C D C 13......................................................................................................... 93

4-17. Conversion of PPE-NEt2/OC9(20)[54] to cationic polyelectrolytes........................ 94

4-18. Normalized UV-Vis absorption and solution photolumninescence for PPE-OC9(20)
type polym ers. .................................................................................................... 97

4-19. TGA thermograms for neutral and protonated PPE-OC9(20) under N2.................. 98








mm : .. ": ... h
...... *:. T + .. '.




S*' .4. .I .. :. .
.














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

SYNTHESIS OF VARIABLE BANDGAP CONJUGATED POLYELECTROLYTES
VIA METAL CATALYZED CROSS-COUPLING REACTIONS

By

Michael Brian Ramey

May 2001

Chairman: Dr. John R. Reynolds
Major Department: Chemistry

Metal catalyzed coupling reactions such as the Stille, Suzuki, and Sonagashira

(Heck) have become useful tools for the organic chemist over the past two decades for

the formation of carbon-carbon bonds. Tolerance of functional groups, reasonable

reaction temperatures, and high yields have allowed these techniques to be applied to the

synthesis of conjugated polymers. These syntheses offer access to a wide variety of

conjugated backbone structures that have previously been difficult to reach using

traditional polymerization techniques.

Poly(p-phenylene) [PPP], poly(p-phenylene-co-thiophene) [PPT], and poly(p-

phenylene-co-ethynylene) [PPE] electrolytes have been prepared by using one of the

aforementioned coupling techniques. A methodology was applied whereby charge neutral

polymers were first synthesized and then converted to the corresponding cationic

polyelectrolyte. This "pre-polymer" technique allows for studies comparing neutral

polymer properties (i.e., absorption, luminescence, solubility) to those of the






polyelectrolyte. Significant changes in the polymers' visible absorption and emission

wavelengths occur between the differing backbone structures. The polyelectrolytes'

optical transitions are shifted to higher energies (blue-shifted) versus the absorption and

emission of the neutral version within the same polymer backbone type.

The effects of halogenation of the monomer, solvent type, and palladium catalyst

on the molecular weight were determined for each set of neutral polymers by monitoring

chain extension by gel permeation chromatography. In the case of the PPP derivatives, it

was found that the Suzuki polymerization proceeds the fastest to maximum molecular

weight in a DMF / aqueous media using PdCl2(dppf) catalyst with di-iodinated

monomer. Polymerizations using di-brominated monomers reached similar molecular

weight values but only after longer reaction times. Polymer chain growth in this system

was limited by the precipitation of polymer from the reaction solution and not the

reactivity of the halogenated monomer. PPT polymers synthesized using the Stille

reaction proceeded to highest molecular weight values in anhydrous DMF using

PdC12(PPh3)2 catalyst and di-iodinated monomer. Triethylamine / THF solvent systems

using PdCl2(PPh3)2 catalyst with a small amount of Cul co-catalyst and di-iodinated

monomer were the best conditions for the PPE Sonagashira polymerizations. Di-

brominated monomers were ineffective in reaching polymeric materials when used in

either Stille or Sonagashira polymerizations. The conversion procedure to the

polyelectrolyte was determined to be sufficiently mild not to induce breakages of the

backbone, thus allowing the molecular weight characteristics foihe neutral species to be

roughly applied to the polyelectrolyte.






xii .:*r*
.. .. ..


A : .. NA:. ... ..:. r :" : ": .. .. .. .
..... ,", : :,. ..\. : '.* :*:*'. ,:* r ::;i { z ;!!'^d


.:.'*












CHAPTER 1
INTRODUCTION


The Origination of Polymer Chemistry

Over the past 100 or so years, polymer science and chemistry have evolved from

early rubber and Bakelite type chemistries to extensively characterized and

commercialized materials. Looking back on the early evolution of this branch of science,

today's observer would find vigorous debates on the exact nature of polymers: were they

linear polymers held together in long chains by covalent bonds or merely

"agglomerations" of smaller molecules held together by ionic forces? Today, we know

that they are indeed based on the first principle as proposed and defended by Staudinger.'

Necessity proved to be the mother of invention as the need to replace natural

items such as silk (Nylon 6,6) and rubber (cis-1,4-polybutadiene), imported from foreign

countries to the United States, was of utmost importance during World War I as the

conflict threatened to cut off supplies. From these beginnings, the study and everyday

use of man-made polymers has exploded (possibly best exemplified by the whispering of

the line "Just one word: plastics" in the 1967 Hollywood movie The Graduate).

Synthetic polymers are a major cornerstone of the entire industrial chemical world and

basic research on these materials has enabled scientists to understand natural polymers,

such as proteins, on deeper levels than ever before. With such broad and sweeping

applications and variations throughout polymer chemistry, a complete overview of the

science would be impossible; therefore, a "guided tour" will be presented herein outlining



" ". .... ... :, I








the buildup of repeat units and properties within conjugated polymer systems (materials

with alternating single and double/triple bonds). These polymers have exciting new

applications for optical display markets, which could never have been envisioned during

the early days of the science.


Background and Theory of Conjugated Polymers

One of the simplest organic molecules is the two carbon molecule ethene,

CH2CH2, which exists as a gas under standard temperature and pressure. Polymerization

of the molecule leads to long chains of covalently bound two carbon units, -(CH2CH2)-,

termed polyethylene. As the number of covalent bonds increases, the material moves

through liquid (20 repeats), waxy (100 repeats), brittle plastic (200 repeats), and tough

plastic (>200-300 repeats) stages of mechanical properties. In the 100-200 repeat unit

regime as chain lengths become long enough to entangle, a material with plastic qualities

emerges that bridges the gap between crystallites to form tougher materials.

Most polymers have a minimum molecular weight threshold where mechanical

properties do not change greatly with additional coupling. Higher molecular weights

may produce polymers that are more difficult to process due to poor solubility or very

high melting temperatures. A balance must be achieved for each particular polymer

system to make good materials that can be molded for use. As more complicated

polymer systems are envisioned, several factors control the molecular weight to solubility

ratio. Side chain branching from the backbone of linear polymers reduces ordering and

lowers the degree of crystallinity and has become a standard method of increasing

polymer solubility. Incorporation of unsaturated bonds or aromatic rings in the backbone

reduces rotational freedom of the polymer chain, thereby stiffening the sain.

: .. 0 :.







Functionalized polymers capable of hydrogen bonding interactions can have lowered

solubility as well.

Polymers that form extended, ribbon-like structures in solution rather than a

random coil conformation are termed rigid-rod polymers. Such polymers are exemplified

by poly(p-phenyleneterephthalamide) 1, poly(benzobisthiazole) 2, and poly(p-phenylene)

3, shown in Figure 1-1. Polymer 1 maintains its rigid-rod nature by hydrogen bonding

between chains and polymers 2 and 3 maintain the same nature by being entirely

conjugated. The conjugated polymers have the unique property of being electroactive,

meaning they have dielectric and spectral properties (such as luminescence) that depend

on applied voltages. Because of the electroactive nature of conjugated polymers, they

have become a major focus of research over the last 20 or so years. It is easy for one to

focus solely on the optical properties due to the visual nature of humans; however, it is

important not to forget mechanical property considerations, because solubility and

processing difficulties must always be dealt with in these systems.







J n
1 2 3

Figure 1-1. Structures of poly(p-phenyleneterephthalamide) (1), poly(benzobisthiazole)
(2), and poly(p-phenylene) (3).


Bandgap: From Dienes to Extended Conjugation Systems

The simplest of the conjugated polymers is polyacetylene, -(CH-CH)-, which was

synthesized by Ziegler-Natta polymerization of the monomeric gas.2 The material is of








low density, fibrous, and has few defect sites.3 Polyacetylene is intractable due to its

extensive conjugation and rigid nature. Just as mechanical properties build up with

additional coupling of monomer to polymer chains, electronic properties of n-conjugated

polymers grow analogously. Hickel Molecular Orbital Theory provides a qualitative

description of the behavior of n electrons of planar conjugated systems and can be used

to explain the electronic behavior of such systems. The overlap integrals (Sy) for orbitals

perpendicular to one another are considered to be zero.

This method can be utilized to describe the aromaticity in benzene and can be

extended to linear conjugated systems by treating them as giant cyclic structures with

equally spaced carbons. Orbital energies are given by the expression


E= c+2fcos( J) J= 1,2,...,N (1-1)
N+1

where J is the orbital number, counting upward from the lowest-energy orbital J = 1, and

N is the number of carbon atoms (also the number of basis orbitals) in the chain. The

binding energy of an electron to the 2p orbital is related to the Coulomb integral a. The

resonance integral 1 is related to the energy of an electron in the field of two nuclei. The

maximum energy between the lowest and highest molecular orbitals is arbitrarily set at a

constant value of 43. Figure 1-2 shows the application of the Frost's circle4 mnemonic to

illustrate to energy levels for cyclobutadiene and benzene.

As the number of linearly combined atomic orbitals increase (corresponding to

larger ring size in the Frost circle), it becomes clear that the energy difference between

molecular orbitals becomes increasingly small. The energy to excite an electron from the

HOMO to LUMO level would be insignificant relative to the thermal eergy of an' ,:,



... .. .. .. ..
S .. E. .
P., .," .4"'' P .. S:. E









electron. The orbitals would merge into a one-dimensional band, similar to the

conduction bands of metals. Electrons in the highest energy occupied orbitals would be

free to move into the unoccupied orbitals where they would have a high mobility. This

simple model would allow for polyacetylene to be metallic with no barrier to the free

movement of electrons in the system.



relative orbital orbital
molecule Frost's circle molecular orbitals energies type

a 21 antibonding


S} -- a nonbonding


4[ a + 20 bonding


Sa 2 antibonding



a + 2 bonding


Figure 1-2. Application of Frost's circle to illustrate the energies of molecular orbitals
within cyclic systems.



Experiments have proven that polyacetylene is not a metallic conductor in its

neutral state. This is accounted for by analyzing the orbitals at the Fermi level. The

Fermi level is the energy level which has a 50% chance of being occupied by an electron

and represents the midpoint in energy of a symmetric half-filled band. The molecular

orbitals at the Fermi level are close enough in energy to behave as if degenerate. The

Jahn-Teller theorem5 predicts that when degenerate orbitals are unevenly filled with


... i.. ....







electrons, the energy of these orbitals change as a consequence of a symmetry lowering

vibration. The orbitals become nondegenerate and the total energy of the system is

lowered.

In solid state physics terminology, the Jahn-Teller effect is known as a Peierls

distortion6 and opens a gap in the pz band which physically distorts the polymer chain to

achieve a lower energy. Figure 1-3 graphically represents the effect of the Peierls

distortion on the band structure and density of states (DOS) of polyacetylene. Figure 1-

3a,b would exemplify a metallic conductor with no energy difference for electrons to

migrate into the unfilled conduction band. Figure l-3c,d demonstrates that as adjacent

carbons along the polymer chain dimerize, alternate single and double bonds are formed

as a discrete energy/band gap develops (Eg). The p, band is broken into an empty

conduction and a full valence band. Polyacetylene is a semiconductor (a < 10-5 S cm'1)

with a band-gap (Eg) of 1.4 eV.7

S Polyacetylene can reach conductivities on the order of 104 S cm' by the addition

of electrons into the conduction band or removal of electrons from the valence band,

termed n-doping and p-doping, respectively.8 These processes result in further structural

changes in the system and defects known as solitons are formed.9 A negative soliton

corresponds to a resonance stabilized carbanion and a positive soliton corresponds to a

resonance stabilized carbocation. These charged solitons move under the influence of an

applied electric field.10

From the initial discoveries concerning the conductive and redox chemistry of

polyacetylene, the field of electroactive polymers has exploded into one of the most



: i..,, : '" .. :.
~J ... : : : :' .:" i : .,






active research areas of polymer chemistry. The importance of the early work on
polyacetylene was confirmed by the awarding of the 2000 Nobel Prize in Chemistry to


EEg


D(E)
d


Figure 1-3. Band structure and density of states (DOS) diagram of a simple one
dimensional metal (polyacetylene) prior to and after a Peierls distortion.
a) Band structure prior
b) DOS prior
c) Band structure after Peierls distortion
d) DOS after Peierls distortion.
Eg is the bandgap, which for a semiconductor such as polyacetylene is twice the
activation energy for conduction.


1








those most responsible for the early work, Alan J. Heeger, Alan G. MacDiarmid, and

Hideki Shirakawa. The door for a myriad of creative syntheses to incorporate aromatic

hydrocarbons, heterocycles, vinyl, and ethynyl groups into the backbone of it-conjugated

polymers was opened by the initial work on polyacetylene. Important properties not

envisioned with the discovery of polyacetylene, such as electrochromism and

electroluminescence, have evolved with these newer materials. The properties and

syntheses of these materials are much too varied and exciting to sufficiently cover in this

dissertation, but an excellent starting reference for investigating these materials is The

Handbook of Conducting Polymers." Focus will be placed, herein, on the property of

electro/photo-luminescence and the synthetic application of palladium (0) catalyzed

coupling reactions to the preparation of conjugated polymers.

Luminescence: Photo- and Electro-

Much of the discussion and graphical representations presented in this

introduction to the electroluminescence of conjugated polymers is based on the review of

the topic by Richard H. Friend and Neil C. Greenham in "Electroluminescence in

Conjugated Polymer" in The Handbook of Conducting Polymers (see Ref. 11). Please

refer to this reference for a more complete discussion of the technical specifics for

construction and properties of light emitting diodes (LED's).

Electroluminescence is the generation of light by electrical excitation and was

first reported for an organic semiconductor in 1963 by the observed emission of light

from single crystals of anthracene.12 Studies on these simple electroluminescent organic

semiconductors established that the process responsible for the emission of light requires

the injection of electrons from one electrode and holes from the other, the capture of one




: E::.. .. .. ...








by the other recombinationn), and the radiative decay of the excited state (exciton). The

first example of electroluminescence from a conjugated polymer was first reported in

1990 using poly(p-phenylenevinylene)[PPV] as the semiconductor between metallic

electrodes.'3 In LED's, a voltage bias is placed across the electrodes at a sufficient level

to achieve injection of positive and negative charge carriers from opposite electrodes and

upon migration, the positive and negative charges combine to form an exciton which

subsequently releases energy as light.

The excitation to form an exciton may also be achieved by exposing the polymer

to light of a wavelength that matches its absorption maximum and is termed

photoluminescence. A singlet exciton is generated by photoexcitation across the

polymer's 7 n* bandgap, and radiatively decays to emit light. Emission spectra for the

same polymer excited either electrically or photolytically are usually very similar,

indicating that the excited state responsible for light generation is identical for both

methods of excitation.

"Polaronic" excited states are formed along the polymer due to the ability of

polymers to rearrange chain geometry to reduce the strain that can be produced by the

charged excitations (excitons). Polyacetylene has a degenerate ground state allowing

formation of soliton-like chain excitations with a nonbonding n level in the middle of the

n n* semiconductor gap.14 In polymers with nondegenerate ground states, the two

senses of bond alternation do not have equivalent energies. The charged excitations of a

nondegenerate ground-state polymer are termed polarons or bipolarons and represent

localized charges on the polymer chain. Figure 1-4 shows the nondegeneracy of PPV

along with a schematic representation of an intrachain exciton. Two nonbonding midgap




10


"soliton" states form bonding and antibonding combinations, producing two gap states

symmetrically displaced about the midgap (see Figure 1-5). The levels can be occupied

by 0 to 4 electrons giving a positive bipolaron (bp2+), positive polaron (p'), polaron

exciton, negative polaron (p), or negative bipolaron (bp2).






ground state excited state
~--



exciton

Figure 1-4. Geometrical relaxation of a PPV chain in response to photo- or electo-
excitation.





it conduction band


-mn 'e-t l-e
lu, minescence .


bp2 pl I- potaron- m* P" bp2"
n valence band exoiton

Figure 1-5. Polaron, bipolaron, and singlet exciton energy levels in a non-degenerate
ground-state polymer.'



-* Si let and triplet excitons have been shown to exist in conjugae polymers.

Taking into account both Coulonbic and electron-lattice interactions, the tplet exciton
s o ttVI'.- ";citon..

and singlet exciton are no longer of the same energy nor of thee se sife. e triplet

exciton becomes more localized than the singlet excitonwhic my extend :over several
..... .. .4.... .. .

"AF
..' ... ..* ... JI: :.
.... .. ? ::.. .. : ,.::. ,.: =;...:i a. ,,. .





11


polymer repeat units. Calculations have shown that the triplet exciton is stabilized by

0.65 eV with respect to the singlet exciton and is localized over not much more than a

single polymer repeat unit for PPV.15 Figure 1-6 shows the relative arrangement of

ground and excited state energies for a conjugated polymer including the experimentally

measured higher energy triplet (T*). Typically, excitation occurs to a singlet exciton that

undergoes some vibrational release of energy and then returns to the ground state via the

release of light energy. The relaxation before emission of light results in the energy of

emitted light being of slightly lower energy than the energy of the 7 to 7T* level (Stoke's

shift).


singlet


triplet
T


inter-
1 -system induced absorption
crossing



T
absorption luminescence

S _

Figure 1-6. Electronic transitions in a conjugated polymer (i.e. PPV) showing both
singlet and triplet states.


Conjugated Polymers for Electroactive Applications

Control of the n to t* energy gap of a conjugated polymer is of utmost

importance in order to tune the wavelength of emitted light through the visible light

region. The energy gap can be modified by directly changing the type of conjugation


;4. .-.... .
A===. .X="..
,!'!,L*, ,,
E.. ..:.. ._* "C











Table 1-1. Brief Summary of Emission Wavelength for Differing Conjugated Polymer
Structures.

Structure Name Emission peak (nm)


otn


Poly(p-phenylene)
PPP


Polyalkylfluorene


" n


R R








P n





n




n
R


Poly(p-phenylenevinylene)
MEH-PPV





Poly(p-phenylenevinylene)
PPPV



Poly(3-alkylthiophene)
P3AT


along the backbone, addition of side-chain groups with electron donating or electron

withdrawing substituents, or disruption of conjugation length by insertion of non-

conjugated segments. The more electron rich a system is, the farther into the lower

energy, red emission portion of the visible spectrum it will be. Electron deficient

polymers will emit in the higher, blue emission portion of the spectrum.


420-465


605






570




460-560


I








Blue emission is found in poly(p-phenylene) (PPP),16 polyalkylfluorene,17

fluorinated polyquinoline,'8 PPP-based ladder copolymers,19 and lower gap polymers

with interrupted conjugation.20 PPV gives emission in the yellow-green light region and

the emission color can be moved toward the red by substitution with electron-donating

groups such as alkoxy chains at the 2- and 5- positions on the phenyl ring.21 The very

electron rich heterocycle containing polyalkylthiophenes emit in the red region of the

spectrum.22 Table 1-1 lists the polymers mentioned above with their corresponding

emission peak in nanometers. It should be noted for exact LED configuration the

reference for each type of polymer should be referred to as the negative electrode and

transport layer material in solid state emitting devices can affect emission characteristics.

The references listed represent the initial pioneering studies done on each material in the

early 1990's.

Many variations and methods of device construction have been attempted over the

last decade with the above polymer types and others to improve device output.

Discussion of all the variations in LED construction will not be presented here due to the

focus of this research being aimed at the syntheses of new conjugated polymers. In

particular, a focused discussion of the palladium(0) catalyzed Suzuki, Stille, and

Sonagashira coupling reactions will be conducted.


Palladium(0) Coupling Reactions

An important component was added to the toolbox of the synthetic organic

chemist in the early 1970's, by the development of cross coupling reactions involving

metal catalysis of organometallic species. Equation 1-3 illustrates the simple principles

involved in a cross coupling reaction. R and R' are typically sp2 hybridized carbon


.. ;i" .." "








R-M + R'-X -- R-R' [with Pd(0) catalyst] (1-3)

species, M is a metal (tin, boron, etc.), and X is a halogen or triflate. Palladium catalyzed

reactions of Grignard reagents was first reported by Yamamura et al.23 and then expanded

into a synthetically versatile method by Negishi et al. to include organoaluminum,24

zinc,25 and zirconium reagents.26 Many other organometallic reagents have been used as

nucleophiles for the cross coupling reactions including organolithiums,27

organostannanes (Stille),28 organosilicon,29 and organoboron (Suzuki)30 compounds.

Terminal alkenyl (Heck)3" and alkynyl (Sonogashira)32 carbons are also effective for the

reaction, though not organometallic species. Several good reviews are present in the

literature dealing with the reactions, mechanisms, and synthetic utilities.33


General Catalytic Cycles and Mechanism

All of these cross coupling reactions are mechanically and synthetically similar

and the general catalytic cycle will be described in this chapter. More focus on reaction

specifics for the differing coupling reactions will be provided in subsequent dissertation

chapters in which the chemistry involved utilizes the particular method. All of these

coupling reactions proceed through a three step cycle involving 1) oxidative addition of

an aryl halide (or other sp2 C-X species) to Pd[O]; 2) transmetallation, wherein a second

aryl group is transferred from the metallated species to Pd; and 3) reductive elimination

of a biaryl species (see Figure 1-7). If difunctional metallated and aryl halide reagents

are used, oligomeric and polymeric materials may result. Electron withdrawing groups

facilitate the oxidative addition step, while the nature of the halide or leaving group

affects the reaction rate following the trend I>OTf>Br>>C. The transmetallation step

may be rate limiting if the metallated species is sterically hindered.


: ;..': :? :: .."' .
::' : : :*.f. ** ::- -: ? ^
:. : .. ...... ,
* *'< "1' .. : ... .. .:. <1,
.:


; ;. f
I*
''"











Ar-Ar rU 4 -s ArX

reductive oxidative
elimination addition

L Ar L Ar
Pd P
L Ar' L/ X





transmetallation



M-X Ar'-M
X = I, Br, etc.

M = B(OR)2, SnR3, etc.

Figure 1-7. General catalytic cycle for Pd(0) cross coupling reactions.



Reactions are conducted under anaerobic conditions in a variety of solvents such

as THF, DMF, and toluene. For the Suzuki reaction, water and base are added to

accelerate the formation of a more active boronate anion for the transmetallation step;

otherwise the other methods are performed in dry solvent. Pd(II) catalysts such as

PdCI2(PPh3)2 are usually employed in the reactions due to their general storage and

handling advantages over Pd(0) catalysts, such as Pd(PPh3)4, which are air and moisture

sensitive. When using a Pd(II) compound, the reduction of the Pd(II) species to Pd(0)

must occur before the cycle can begin. The exact nature of this conversion is debated but

may include the homo-coupling of the Metallated species. Ligands present on the Pd aid

. .-









in solubility and activity of the catalyst, but can undergo ligand transfer instead of the

desired aryl moiety, particularly in the case of triphenylphosphonium ligands.

Often, Stille and Suzuki polymerizations can be applied to the same desired

polymers and general guidelines should be followed in making the best choice. The

chemistry behind the synthesis of aryltin compounds used in Stille reactions involves the

use of chlorinated alkyl tin reagents which are toxic and re-generated during the course of

the reaction. Therefore, if possible the Suzuki reaction should be used. Boronic Suzuki

reagents and the salts formed during the catalytic cycle are relatively "harmless." The

drawback to the Suzuki reaction is that for many electron rich aryl groups, boronic esters

or acids are much too unstable to withstand the numerous couplings needed for

polymerization. Obviously, the Heck and Sonogashira reactions are applied specifically

to the formation of vinylene and ethynylene linkages and are not alternatives to many

Suzuki or Stille routes. The reagents for each are fairly stable organic and the by-

products of the catalytic cycle are mineral acids.

The palladium (0) reactions hold several advantages over other polymerization

techniques when used to make conjugated polymers. Many free radical polymerizations

convert activated double bonds to single bonds in order to achieve the couplings, while

step growth polymerizations often involve the coupling of carbon atoms to heteroatoms

with an associated release of a small molecule such as H20. The Pd catalysts are

generally stable and tolerate most functional groups, allowing a wide range of

polymerization possibilities. Many complex repeat unit structures can be constructed by

mixing different ratios of metal and halogenated reagents. Of course, ovieal a j

stoichiometric balance (1:1) of total halogen to metal ftnc~aityo us be as
" ,. "" .. h. .. ... i : .
.. .... .... .. *.
~ j ~ ~ .E -, JIi









these are step growth polymerizations. Catalyst residues and by-products are easily

removed from the polymer product.

In the synthesis of conjugated polymers, several factors influence ultimate

molecular weight properties. A balance must be maintained in a polymerization between

a solvent that will keep the polymer chain in solution, so that additional couplings can be

performed, and that will also solubilize the Pd catalyst so that it remains active. Chain

growth is terminated by premature polymer precipitation. In general, DMF, THF, and

toluene are effective solvents for the coupling reactions, with DMF able to stabilize the

catalysts the most due to its coordination ability. The polarity of the solvent should

match the polarity of the polymer to best keep it in solution. Temperatures must be

carefully monitored as excess thermal energy can degrade the catalyst and promote the

degradation of the active functionalities at the end of the polymer chains, thereby

terminating chain extension. Temperatures at or below 80 C are commonly used.


Conjugated Polyelectrolytes

As mentioned earlier, one important issue in the conjugated polymer field is that

of processability. Traditionally, branched or long alkyl side chains are added to

conjugated polymers to increase solubility. Although this is effective, chlorinated and

high boiling solvents are often necessary to dissolve the polymers. One approach to

overcoming this difficulty is to create polar conjugated polymers that are water soluble.

The interesting luminescent properties mentioned previously will still be present, but now

the polymers may be processed from the more environmentally and industrially friendly

solvents, such as ethanol, water, etc. Side chains can be functionalized with carboxylate,

sulfonate, and quatemized ammonium groups to achieve the water solubility.


.:.
-. s '*:' ...








There are also numerous chain extension and folding effects to be studied that are

unique to polyelectrolytes. Flexible polyelectrolytes have been the focus of a

considerable amount of research for many decades.34 Decreasing the ionic strength of a

dilute aqueous solution of polyelectrolyte leads to an expansion of the polymer coils and

an increase of solution viscosity due to strong intra- and inter-molecular forces.

Separation of the intra- versus inter- molecular forces is a difficult experimental task and

only recently has the understanding of the single chain behavior of flexible

polyelectrolytes been achieved by Monte Carlo simulations.35

Conjugated, stiff-chain polyelectrolyes remain in an extended conformation

regardless of the ionic strength of the solution. Effects observed from lowering the ionic

strength of the system must therefore be due to intermolecular forces. Conjugated

polyelectrolytes represent interesting models for studying the screened coulombic

interactions in polymeric systems. Interesting applications may also be available for

these materials in membrane manufacturing.36 Specifics and references for literature

examples of conjugated polyelectrolytes synthesized by palladium (0) catalysis will be

given in the introduction to Chapter 2.


Scope of the Dissertation

This body of work focuses on incorporation of quaternized 2,5-dialkoxyamine-

phenylene or quaternized 2,5-dialkylamine-phenylene salt moieties into the backbone of

conjugated polymers. Suzuki, Stille, Sonagashira (Heck), and ADIMET polymerization

techniques will be used to synthesize neutral polymers of the following types: poly(p-

phenylene)[PPP], itily(p-phenylene-co-thiophone.)[PPT], and poly(p-phenylene-co-

ethynylene)[PPE], whereby the phenylene portion of the repeat u it is initially

*,L ...... :: .. .
:- : .. i : ... *,:''.: ;( i : :.:: :\ i
4 : E.., .
.. .;. ., .. ..:: :.::. '. :. ::::..








synthesized with neutral alkoxy-triethylamine or alkylbromide side chains. These neutral

polymers can be analyzed using traditional techniques (GPC, NMR, etc.) and will possess

absorption and luminescence wavelengths that vary over the visible wavelength range

based on the electronic makeup of the backbone.

Alkoxy-triethylamine containing polymers were treated with bromoethane to form

the cationic dibromide salt of the original polymer. Likewise, the alkylbromide

containing polymers were treated with triethylamine to achieve the desired

polyelectrolytes. Molecular weight characteristics of the neutral polymer can be

approximately applied to the polyelectrolytes, since the treatments of the neutral polymer

do not break backbone linkages. Optical properties will be extensively investigated

focusing on the emission, absorption, and electrochromic responses from both the neutral

and water soluble polymers in solution and as prepared films


I .. .












CHAPTER 2
CATIONIC POLY(p-PHENYLENE)'S


Introduction


Early Synthetic Attempts

Poly(p-phenylene) (PPP) has long been a synthetic target for polymer chemists

due to theoretical calculations and observations on ill-defined materials37 that show PPP

to possess good mechanical strength and high chemical resistivity.38 Possibly, the most

important property of PPP is its ability to be used as a blue emitter in electroluminescent

devices.39 The advantages of using a polymer to emit light in the consumer electronics

industry are immense, as the more numerous polymer processing techniques allow for the

creation of "flat panel" computer and high definition television screens unavailable with

traditional materials and techniques. A thin film of PPP is placed between a high work

function anode (indium tin oxide coated glass) and a low work function cathode

(calcium). Under appropriate forward bias, holes and electrons are injected into the

polymer film, resulting in the formation of positive polarons onone side of the film and

negative polarons on the opposite side. The polarons migrate toward each other and a

singlet exiton is formed resulting in the emission of blue light.

Two major factors have hindered the synthesis of PP. As the.-piber of rings in

an unsubstituted, linear "pure PPP" typ polymer increase, solulit optyef resitik .,

chain diminishes quickly, leading to an insoluble, intractable. pd-- j t 6 little r

no use. However, the methodology applied to solubiwling PPP ani utin


91, +w !:. T N A Hs....








that do not reflect the characteristics of "pure PPP". Thermal, mechanical, and chemical

stability are reduced and the optical absorption and emission wavelengths are shifted

from the expected values. Nevertheless, the molecular weight enhancements and

solubility of resulting substituted PPP's often outweigh the property differences between

themselves and "pure PPP".

A second hindrance to PPP synthesis is that traditional polymerization techniques

are not designed to grow a chain via carbon-carbon bond formation, but typically via

carbon-heteroatom (oxygen or nitrogen) coupling. Often the somewhat "exotic" methods

used to create PPP actually enhance side reactions leading to structurally poor polymers.

Electrochemical polymerizations have been attempted both oxidatively with 1,4-

dialkoxybenzenes40 and reductively with 1,4-dihalobenzenes in the presence of a nickel

catalyst.41 Chemical oxidation polymerizations have been conducted with cupric chloride

(Figure 2-la).42 Thermal conversion of radically43 or transition metal polymerized4

protected 5,6-dihydroxy-l,3-cyclohexadiene to unsubstituted PPP overcame solubility

difficulties with soluble "pre-polymer" intermediates that can be processed and

subsequently converted to "pure PPP" (Figure 2-lb). Thermal cyclization of enediynes

and o-phenyldiynes gave PPP's and poly(l,4-naphthylenes), respectively (Figure 2-lc).45

Nickel catalyzed Grignard couplings of 1,4-dibromobenzene have also been performed

by Yamamoto et al. (Figure 2-1d).46 The Grignard coupling route provided structurally

pure PPP oligomers. This mild route was promising, but termination by inherent

chemistry or precipitation of the growing polymer negated higher molecular weights.

Attachment of alkyl side chains led to a more homogeneous polymerization and higher

degrees of polymerization. Nickel catalyzed homocoupling of dichloro-,47







di(methanesulfonyl)-,48 and di(trifluoromethanesulfonyl) benzenes49 in the presence of

excess zinc have afforded functionalized PPP's (Figure 2-le,f ).


1. CuCI2 I AICIa / 02
2. MeOH / HCI


R*t .heat
S-2HOR
RO OR


R R

" f46h


RO OR
RO OR


R R

\/~


R
Br- -Br M.
R


R
Br- /-MgBr
R


Ni(O)
cat.


R
Cl CI
R


Ni (0) cat.
Zn


R1 R
RO2SO- OS02R N ct.
R = CH3, CF3

Figure 2-1. Synthetic methods to poly(p-phenylene).


Suzuki Couplings

A major improvement in PPP synthesis came in 1989.when Rehahn and

coworkers applied the more reactive Suzuki coupling reaction methodology to the:



L M.. .... .. .::.. .::
.. ~ : .. ::J :; ._ ; :,,411








polymerization. 5051 A-B polymerization of 4-bromo-2,5-dialkylbenzeneboronic acids

and AA/BB polymerization of 1,4-dibromo-2,5-dialkylbenzeneboronic acids was

performed (Figure 2-2). Chain lengths of 100 rings were achieved leading to

processable, substituted PPP's.52

The success of the Suzuki reaction with its use of less electropositive boron

reagents, high yield couplings, and tolerance for mixed aqueous / organic solvent systems

opened the door to a variety of functionalized PPP's hitherto unreachable. One of the

most interesting sub-fields to arise from this methodology was the synthesis of

conjugated, rigid polyelectrolytes. The first rod-like polyelectrolytes were reported in the

early 1980's and were based upon poly(l,4-phenylenebenzobisoxazole) and poly(l,4-

phenylenebenzobisthiazole).53 Careful incorporation of anionic or cationic functionality

into a PPP yields a material that possesses the beneficial properties of a conjugated

polymer with the aqueous solubility and processability of a polyelectrolyte. The

environmental utility of aqueous processing techniques applicable to polyelectrolytes is a

potential advantage of these materials for use in an industrial setting. Carboxylate

(Figure 2-3a,b),54 sulfonate (Figure 2-3c),55 and sulfonatopropoxy groups (Figure 2-3d)56

have been used to create anionic PPP polyelectrolytes.

R R R
Br 1. n-BuLi Br H Pd (0) cat. (a)
Br Br Br &a- -d (a)



R A
S- Pd ) Rcat.
Br Br + H }0 -c (b)
y_0HO H O aq.b|e n
R R
a.. .
Figure 2-2. Suzuki coupling approaches to substituted poly(p-phenylene).


I ... 4
..O

..'> :.::;i... ii : : .""'47 .* ""r:













COOH (CH2) n R


n
HOOC (CH2)6 R
(a) \ (b)



HOOC SO3-


R S03'Na+

n n
R 0
(c) (d)


'038

Figure 2-3. Anionic poly(p-phenylene)'s reported in the literature.



Highly charged cationic ammonium and pyridinium PPP polyelectrolytes were

reported in the mid 1990's by Rehahn and co-workers (Figure 2-4a,b).57 Dr. Peter B.

Balanda of the Reynolds' research group used an alternate methodology to include

cationic quaternary ammonium salt side chains into a PPP backbone (Figure 2-4c).58

Poly[2,5-bis(2- {N,N,N-triethylammonium -1-oxapropyl)-1,4-phenylene-alt-1,4-

phenylene] dibromide (PPP-NEt3+) was synthesized via a Suzuki protocol. The polymer

was used in the assembly of blue emitting solid state devices via layer-by-layer

polyelectrolyte self-assembly with sulfonatopropoxy PPP. 59 The material also proved

very useful as a buffer layer for hybrid ink jet printed LED's using sulfonatopropoxy

substituted poly(phenylene-vinylenes).60




S, i : .















\ /- -' / n \ --' /- / n \ ^- v- / n
(CH2) R (a) (CH2)6 R (b) 0 (c) PPP-NEt3+
\ (a) r (b)

SB
Figure 2-4. Cationic poly(p-phenylene)'s reported in the literature (R = hexyl).



Due to the important applications available for PPP-NEt3+, it was evident that a

closer inspection of the synthesis, along with scale-up procedures was needed. In

particular, a focused look at a new palladium catalyst with stabilizing ligands and higher

reactivity was a primary concern. Other synthetic investigations to be accomplished were

the effect of the halogenated monomer on the molecular weight of the polymer and the

effect of more unsubstituted phenylene rings in the polymer backbone. With more

unsubstituted phenylene rings, a system that resembles "pure PPP" better might be

created, but problems of solubility could arise also. The results and discussion following

will address these aspects in greater detail.


Results and Discussion


Monomer and Model Compound Syntheses

Previous work had shown that the most promising route for the cationic water

soluble PPP synthesis was to first create a neutral PPP analog and then quaternize the

amine sites post polymerization. Figures 2-5 and 2-6 show the syntheses of 2,5-

diiodohydroquinone and 2,5-dibromohydroquinone, respectively. 1,4-dimethoxybenzene



I.
. V. ....








(4) was iodonated under acidic conditions using potassium periodate, iodine, and a mixed

solvent system consisting of 90:7:3 HOAc/ HzO/ H2S04 by volume with heating to yield

2,5-dimethoxy-1,4-diiodobenzene (5).61 Compound 5 was reacted with boron tribromide

in methylene chloride at -78 oC, producing 2,5-diiodohydroquinone (DIHQ).62 It

should be noted that boron tribromide is a very reactive reagent with large amounts of

HBr gas liberated during the aqueous workup of the reaction. DIHQ is recovered as a

crude brown solid. Recrystallization from THF and hexane affords colorless crystals of

pure product. Both steps are high yielding (81% and 76%) with an overall 62% yield

based on starting material 4. Analysis of the crude material by 'H NMR shows the only

organic product was the desired compound 4. It was later found that use of this brown

material was sufficient for the Williamson etherifications to follow. 90 % yield of the

crude material was obtained.


H3CO H3C I H I
K104,12 BBr3
AcOH/ H20 / H2SO4 MeCl2
OCH3 70 C /12h I OCH3 -78 OC RT OH
4 5 12h DIHQ
81% 76%/

Figure 2-5. Conversion of 1,4-dimethoxybenzene to 2,5-diiodohydroquinone.



2,5-dibromohydroquinone (DBHQ) was synthesized in 40% yield from the direct

bromination of hydroquinone (6) in methylene chloride and acetic acid. The reaction

proceeds through three stages. The initial setup involves the suspension of hydroquinone

in the solvent system. As the first equivalent of bromine is added, the resulting

monobrominated species enters solution and as the second bromine adds to the phenyl

ring, the desired product precipitates out of solution maklia piduct redor la i..A ,


A. ,. .. ; il l H .. .









matter of filtration. The reaction's lower yield is probably a result of some DBHQ

remaining dissolved in the solvent. No attempts were made to recover this "lost"

material. Recrystallization of the slightly pink crude product from a hot 4:1 (v/v) water

to isopropanol solvent solution removed the undesired impurities.



H 2.1 eq. Br2 OH

S MeC2/ AcOH /
HO 6 HO
DBHQ
40%
Figure 2-6. Bromination of hydroquinone in the 2,5 positions.



DIHQ and DBHQ were subjected to Williamson etherification conditions in

refluxing acetone with 2.1 equivalents of 2-chlorotriethylamine hydrochloride (7) and 4.0

equivalents of K2C03 for three days, as outlined in Figure 2-7, to produce the desired 1,4-

dihalo-2,5-dialkoxyamine phenylene monomers, DINEt and DBNEt. Four equivalents

of K2C03 were necessary for deprotonation of the hydroquinone and the hydrochloride

salt of the 2-chlorotriethylamine reagent which was deprotonated in situ. Isolation of the

organic chlorinated amine would be difficult as cyclization to the aziridinium ion would

likely occur. Grinding of the K2CO3 by mortar and pestle, followed by drying in an oven

overnight, generally increased yields by 10%. The monomers were isolated and

recrystallized twice from methanol / water to achieve maximum purity and dried over

CaSO4 under vacuum to ensure dryness for the accurate mass measurements necessary

for step growth polymerizations. DBNEt was recovered in lower yield due to larger

amounts of material being lost during the recrystallization steps.




... .. .
..' ."iii N .. .* ,"* "s i.'"'1 *'. r ."" "







Figure 2-8 outlines the preparation of various boronic reagents to be used in

conjunction with DBNEt and DINEt in the Suzuki polymerizations to follow. The

general reaction for all boronic species proceeds via the formation of the di-Grignard

reagent of dibromo-benzene or dibromo-biphenyl,63'6 followed by quenching with

trimethyl borate. The boronate intermediate can be treated with aqueous acid to form the

diboronic acid or with neopentyl glycol in a transesterification manner to produce the

diboronic ester. Drying of the hydroscopic boronic acid is troublesome, and with the

exact mass balance requirements necessary for polymerizations, the easily stored and

purified boronic ester was preferred. The reactions are carried out in one pot with overall

yields ranging from 30-40 %. Isolating the boronic acid, followed by transesterification

using benzene to azeotropically distill off the H20 by-product did not improve yields

substantially (5% gain).



N

OH
-1 /2 N 4 eq. K2CO
+ 2.1 eq.N HCI x
acetone/ reflux
HO 7 3 days
C'


0
X Product %Yield
I DINEt 75
Br DBNEt 38

Figure 2-7. Williamson etherification of DIHQ or DBHQ.









BrBr HO > B B
2.2 eq THF B(OCH3)3 HO 0 0
or + Mg reflux 30% 8
Br -rBreflux


35% 9

Figure 2-8. Synthesis of di-boronic phenylene reagents for use in Suzuki couplings.


Figure 2-9 outlines the preparation of a three ring model compound that was used

as a guide for assigning peaks in the 'H and '3C NMR of subsequent polymers and also as

a standard for luminescence sensing studies conducted with Dr. Kirk Schanze and

Benjamin Harrison at the University of Florida.6 Phenylboronic acid and Pd(OAc)2

were used as purchased from Aldrich Chemical Company. Contamination of the product

with Pd(0) does occur when using Pd(OAc)2, as it lacks solubilizing ligands to keep the

catalyst from precipitating. This will be a more difficult issue to address in the polymer

syntheses to follow, but the contamination could easily be removed from the low

molecular weight compound, 10, by the addition of decolorizing carbon and filtration

through sebaceous earth (Celite). Quaternization of compound 10 was achieved by

stirring in THF and bromoethane at 40 oC for 3 days. During the course of the reaction,

the desired product, 11, precipitated out of solution. NMR peak values for both can be

found in Chapter 5 (Experimental) of the dissertation. As expected, compounds 10 and

11 display extreme solubility differences. Compound 10 is soluble in relatively non-

polar solvents such as halogenated organic (CHCl3 and CH2CI2) and the more polar

THF, while compound 11 is soluble in very polar solvents such as acetonitrile and water.


.. I.







Both 'H NMR integration and elemental analysis (22.54 % Br) indicate a nearly

quantitative level of quaternization.


Neutral Polymer Syntheses

The general Suzuki polymerization is outlined in Figure 2-10. The

dialkoxyamine-dihalogenated benzene monomer, boronic reagent, Pd catalyst of choice,

and mild base such as K2C03, Na2CO3, or NaHCO3 are stirred in a mixed aqueous /

organic (THF, DMF, acetone) solvent system with heating to 70 oC. Special care is taken

to ensure that the reaction vessel and solvents are fully degassed with Ar prior to addition

of the catalyst and the reaction conducted under a blanket of the inert gas. Atmospheric

02 in the reaction may contribute to oxidation of the Pd catalyst and decrease its catalytic

activity and/or increase the rate of homocoupling of the boronic reagents.66





0 o
HO Pd(OAc)2
/ \ + 2.2 eq
SHO DMF/H20
K2CO3 10
DINEt K 000
S70 70






EtBr
10 }
THF : ,
40C







F: .". 2-9- p k. .t .cto;"P P:.: :
..i .. .. .. ."...



t..g ) .: v..
.. 5.







The original polymerizations were conducted by Dr. Peter Balanda and focused

on the synthesis of PPP-NEt2 These initial synthetic investigations used DBNEt,

Pd(OAc)2 as the catalyst, with DMF, THF, and acetone as solvents. Usable polymeric

materials were synthesized, with DMF polymerizations giving the highest molecular

weights by GPC. Several obstacles remained. Using Pd(OAc)2 as catalyst resulted in the

precipitation of black, metallic Pd into solution and contamination of the polymer.

Removal of this impurity often proved difficult, if not impossible, and some loss of the

polymer was inevitable.
i*


N


+ B
or

x C-0^C


K2CO3
H20
organic solvent

N)


[12]


Pd catalyst
70 C


/N

0



q PPPBP-NEta [13]


N


Figure 2-10. Suzuki polymerizations for neutral alkoxy-amine containing PPP's.


Reagent

DINEt
DBNEt


':""`"""" ` ` --- iZL~:-




32


Kowitz and Wegner published results from Suzuki polymerizations using the

more active dichloro[l,l'-bis(diphenylphosphino)ferrocene] palladium (II) [PdCl2(dppf)]

as catalyst in a THF based solution at room temperature with very high molecular

weights and percent conversion to polymer.67 The methodologies presented in reference

30 were applied to the synthesis of the amine substituted PPP-NEt2.

The synthesis of PdCl2(dppf) was first reported in 1984 by Hayashi et al.68 The

PdCI2(dppf) has two advantages over Pd(OAc)2. The dppf [diphenylphosphino ferrocene]

ligand provides solubility to the catalyst as the polymerization proceeds, thus preventing

contamination of the polymer with black Pd(0). With one objective to increase scale of

the reaction, contamination must be avoided to prevent loss of product during "cleaning"

steps. A second advantage is that palladium catalysts with bidentate phosphine ligands

are more efficient catalysts than those with unidentate phosphines. The bidentate

phosphine ligands create a unique geometry of the catalyst, minimizing the angle

between the chlorine ligands and somewhat lengthening the palladium to phosphine bond

distance. The bond lengthening reduces steric crowding between the phosphines and the

palladium center. The Cl-Pd-Cl bond angle for two common palladium catalysts with

bidentate ligands, dichloro[l,2-bis(diphenylphosphino)-ethane] palladium (II)

[PdCl2(dppe)] and dichloro[ 1,3-bis(diphenylphosphino)-propane] palladium (II)

[PdCl2(dppp)]69, along with PdCl2(dppf) are shown in Figure 2-11. PdCl2(dppf) has the

smallest Cl-Pd-Cl bond angle of the three catalysts (87.80). Experiments by Hiyashi and

coworkers revealed a direct relationship between the Cl-Pd-Cl bond angle and catalyst

efficiency.32 The two chlorine ligands occupy the sites where the species to be coupled

will eventually reside before reductive elimination. The reduced angle leads to a rate




... .
---------i---- I ____."- 11:' 1* IIII 111 I -.. .* ^ ^.- u***= '..








increase in the reductive elimination step, which is often the rate limiting step in Suzuki

couplings, thus increasing the overall rate of the reaction.

Polymerizations of bisneopentylglycol-l,4-phenylenediboronate and DBNEt

with PdCl2(dppf) in THF / aq. NaHCO3 at 75 oC for 3 days yielded improvements over

previous work [PPP-NEtz(dppf)[12]]. A polymer with higher molecular weight,

Mn=18,700 g/mol [compared to 15,900 g/mol for Pd(OAc)2 in DMF polymer PPP-

NEtz(Br-72)[14]], and lower polydispersity index of 1.18 was synthesized (see Table 2-

1). Elemental analysis for the polymers and other compounds discussed throughout this

chapter are shown in Table 2-2. Figure 2-12 shows the GPC trace for PPP-

NEt2(dppf)[12]. GPC traces for the other PPP-NEt2 polymers are similar with retention

time and peak width varying for molecular weight and polydispersity, respectively. Scale

up by a factor of 2 to 3 times the original scale was successful using the PdCl2(dppf)

catalyst as well as prevention of Pd(0) contamination. Data shown in Table 2-1 for the

Pd(OAc)2 polymers was taken from the dissertation of Dr. Peter Balanda. Subsequent

polymerizations conducted using Pd(OAc)z reproduced this data within experimental

errors. It should be noted that the low polydispersity found for the PdCl2(dppf) is an

effect of the polymer isolation procedures, which in all likelihood fractionated off some

lower molecular weight species. Suzuki polymerizations should behave like traditional

condensation polymerizations with statistically governed polydispersities of 2.

It was further believed that the use of the more active iodinated species, DINEt,

would lead to an increase in molecular weight. Using identical protocols, reactions were

conducted to couple DINEt or DBNEt with bisneopentylglycol-1,4-phenylene

diboronate (8) via Suzuki protocol. Both reactions were quenched by precipitation into




r'':i' ;: i";t






P Ph C Ph C Ph
Pd)Ph P CI mGs 0 Ph

Ckd P Fe Pd
P\Ph CI p Ph ph

PdCl2(dppe) PdCl2(dppp) PdCl2(dppf)

Cl-Pd-Cl Bond Angle 94.20 90.80 87.80

Figure 2-11. Cl-Pd-CI bond angle for PdCl2(dppe), PdCl2(dppp), and PdCl2(dppf)
catalysts.


MeOH after 3 hours. GPC results in chloroform (vs. PS standards) revealed low

molecular weight oligomers ( M < 1,500 g mol"', multi-modal ) for the reaction

usingthe dibromonated species [PPP-NEt2(Br-3)]. The reaction using the diiodonated

reagent [PPP-NEtz(I-3)[15]] reached a Mn = 10,900 g mol-1 with a continuous

polymeric distribution. Published results22b using DBNEt in the reaction for 72 hours

showed a Mn = 15,900 g moll' for the resulting polymer [PPP-NEt2(Br-72)[14]]. The

elemental analysis and GPC results are summarized in Tables 2-2 and 2-3, respectively.

Longer reaction times (complete polymerization stopped after 24 hours) with DINEt

[PPP-NEt2 (1-24)[16] ; Mn = 15,300 g moll' ] approached the molecular weight values

reported for PPP- NEtz(Br-72)[14]. The use of DINEt leads to the formation of a

polymer with similar molecular weight properties to PPP-NEtz(Br-72)[14] in a shorter

amount of time. Once the polymer has reached a certain molecular weight, it begins to

precipitate out of solution, stopping polymer growth, and negating the advantages of the

more reactive iodine reagent at longer reaction times.






". :.; :; i: i ; ., ..". .







In order to gain insight into a polymer that mimics "true" PPP more accurately,

PPPBP-NEt2[13] was synthesized (see Figure 2-10). The boronic ester of biphenyl was

coupled with DBNEt using the polymerization conditions determined for PPP-

NEt2(dppf)[12] [PdCl2(dppf), DMF/H20, and NaHCO3]. During the course of the

polymerization, it was noted that the polymeric / oligomeric materials being formed were

precipitating out of solution much earlier than for the PPP-NEt2 reactions. Subsequent

workup revealed only low molecular weight components ( M < 5000 g/mol) for the

isolated polymer as determined by GPC versus polystyrene standards and a high level

(1.21%) of bromine endgroups as detected by elemental analysis. Only 51% of a tan

material was recovered indicating that the precipitating oligomers are causing an

imbalance in the functional groups present in solution. Without a proper balance of

reactive endgroups in step growth polymerizations, chains will be prevented from

growing into high molecular weight polymers. Insolubility was quickly reached in the

growing PPPBP-NEt2[13] system, as evidenced by early polymer precipitation from the

reaction media.

The low molecular weight and solubility problems of the PPPBP-NEt2[13]

system naturally led to the swinging of the experimental pendulum back to more

substituted phenylene systems. A polymer with every phenylene ring substituted with an

alkoxy-amine side chain should be more soluble during the polymerization and the

subsequent quatemized polymer more water soluble. Figure 2-13 shows two reagents

that could be used in a Suzuki polymerization to achieve the maximum substituted PPP.

The synthesis of compounds 17 and 18 was attempted by the reaction of DBNEt with

magnesium turnings or n-butyllithium followed by quenching with trimethyl borate











500


400


300

E
200


100


5 10 15 20
Retention Time (min.)


Figure 2-12. Gel permeation chromatogram for PPP-NEt2(dppf)[12].


Table 2-1. Catalyst effect on the molecular weight properties of PPP-NEt2 polymers.
reaction Calibration M. MP M,
catalyst solvent yield method kgmol-1 kgmol-1 kgmol-1 Mw/Mn


Pd(OAc)2 THF 38% PS 5.0 4.8 19.5 3.91
PPPa 3.9 3.8 12.9 3.29
Pd(OAc)2 DMF 76% PS 15.9 24.3 35.0 2.20
PPP 10.8 15.6 21.5 1.99

PdCl2(dppf) THF 95% PS 18.7 19.4 22.1 1.18
PPP 12.4 12.8 14.4 1.16
Pd(OAc)2 acetone 92% PS 12.6 21.4 28.6 2.27
PPP 8.8 14.0 18.0 2.05


GPC results in CHC13 vs. polystyrene standards.
Pd(OAc)2 data taken from Dr. Peter Balanda dissertation U. of Florida.
Universal calibration using values derived for PPP in THF.






.. .. .,
I.


, ;. ,'.


. .


36




37





Table 2-2. Elemental Analysis results for PPP monomers and polymers.
Species %C %H %N %I %Br Anal. Calcd. for

Theo. 38.59 5.40 5.00 45.30 C18H3oN20212
DINEt
Exp. 38.81 5.53 4.90

Theo. 41.00 5.41 6.83 34.33 C14H22N202Br2
DBNEt
Exp. 41.13 5.44 6.71
Theo. 78.21 8.76 6.08 -C3oH4oN202
PPPmodel
(10) Exp. 78.41 9.56 5.90

PPPmodel+ Theo. 60.34 7.45 4.14 23.34 C34H5oN202Br2
(11) Exp. 61.27 7.67 4.29 22.54

Theo 74.95 8.91 7.28 C24H34N202Bro.026
PPP-NEt2
(dppf)[12] Exp. 75.21 8.94 8.01 0.45

PPP-NEt2 Theo. 74.95 8.91 7.28 0.53 C24 H34N202Br0.026
(Br-72)[14]
(Br-72)[14] Exp. 75.09 8.92 8.05 0.54

PPP-NEt2 Theo. 74.28 8.77 7.22 1.47 C24H34N202Io.045
(1-3)[15] Exp. 67.32 8.42 6.01 1.48

PPP-NEt2 Theo. 74.82 8.83 7.27 0.76 C24H34N202 o.023
(I-24)[16] Exp. 71.85 8.45 6.78 0.77

PPPBP- Theo. 78.60 8.30 6.11 C30H38N202
NEt2[13] Exp. 70.25 8.22 5.75 1.21

C24H34N202
PPP-NE3 Theo. 54.02 7.85 4.63 21.48 1.6 C2H5Br
PPP-NEt3+
[19] 2.54 H20
Exp. 52.35 7.61 4.31 21.40

PPPBP- Theo. 60.27 7.09 8.05 23.63 C34H4aN202Br2
NEt3+ [20] Exp. 65.68 8.05 5.35 11.98










Table 2-3. Effect of DBNEt or DINEt on the molecular weight of PPP-NEt2 polymers.
reaction reaction reaction
polymer solvent type time M, MP M M/Mn
(hours)

PPP-NEt2 DMF/H20 Suzuki 72 15.9 24.3 35.0 2.20
(Br-72)[14]
PPP-NEt2 DMF/H20 Suzuki 3 10.9 13.3 16.6 1.52
(I-3)[15]
PPP-NEt2 DMF/H20 Suzuki 24 15.3 19.5 27.5 1.80
(1-24)[16]


Molecular weight values are expressed in
GPC relative to polystyrene standards.


units of kg mol'.


Figure 2-13. Envisioned boronic reagents for a more substituted PPP-NEt2 polymer.


R

Br- -Br
R


+ B' -B
CB Ke0


Figure 2-14. Pd catalyzed coupling to diboronic reagents for Suzuki couplings.




~ ~ : .' : 5 : !. ..::. [! :* : ....:!: l:


Pd(OAc)2
DMF, heat


R
R







and transesterification with neopentyl glycol. Both attempts were unsuccessful, possibly

caused by an interaction of the amine groups to the trimethyl borate hindering formation

of the new phenyl-boron bond. Grignard and lithiation procedures were effective as

evidenced by a substantial amount of dehalogenated material in the crude isolated

material. Future work could explore using a palladium catalyzed reaction between di-

halogenated phenylene's and diboron pinacol ester (see Figure 2-14) that has been shown

to effectively produce boronic reagents for Suzuki reactions70 as an alternative route to

the desired compound 18.


Polymer Quaternization

Quaternization of the amine sites followed preparation of the neutral polymers.

Synthesis of poly[2,5-bis(2- { N,N,N-triethylammonium }-l-oxapropyl)- ,4-phenylene-alt-

1,4-phenylene] dibromide (PPP-NEt3+[19]) is accomplished by heating the neutral

polymer in a DMSO / THF solution with bromoethane for 3 days (Figure 2-15). 'H-

NMR indicates that a high degree of the amine sites are quaternized (-90%). Elemental

analysis for bromine content also reflects 90% quaternization (see Table 2-2). The beauty

of synthesizing the neutral polymer first is in the ease of traditional polymer analyses that

can be performed. Analysis of charged polyelectrolytes can be a rigorous and difficult

undertaking,especially with GPC due to aggregation and charge interaction with the

column material. Assuming the methods used to quaternize the amine sites are gentle

enough not to break bonds along the PPP backbone or cleave side chains, molecular

weight data corresponding to the neutral polymer should be a good reflection of the

molecular weight of the water soluble version. PPP-NEt3+[19] displayed excellent

solubility in both acidic and neutral aqueous media. Solutions were stable over the time
L. *








frame of days with only minimal precipitation of polymer from solution observed on

samples stored over a month.


EtBr
THF/DMSO
heat


PPP-NEt,


Figure 2-15. Quaterization of PPP-NEt2.


PPPBP-NEtz[13] was subjected to the same quaternization conditions as shown

in Figure 2-15. Complete quaternization of this material was not achieved as the neutral

material was difficult to dissolve in the quaternization media. 'H NMR analysis of the

material was unsuccessful due to the poor solubility in common deuterated solvents.

Elemental analysis (Table 2-2) of the oligomers revealed a 11.98 weight percent of

bromine. Of this amount 10.77% of bromine is due to quaternized ammonium sites and

1.21% is inherent from the parent PPPBP-NEt2[13]. Full quaternization of all amine

sites would require 23.63% bromine. Overall, this indicates that approximately half of

the amine sites were quaternized. The resulting quaternized oligomers were no longer

soluble in CHC13 or THF, but had reasonable solubility on the order of 5 x 10-3 M (based

on repeat unit MW) in warm acetonitrile ot DMSO. Cloudy "suspensions" in neutral

H20 were formed in the 10'3 M concentration range. The polymer was soluble in water

only if the pH was lowered to around 2 or 3.



"-E:L.t. .::
... :" J 'i!'., '. ... ;. ,:.'.:' ... ..


PL-. J n

PPP-NEt3+[1 9]










Physical Properties of PPP Type Polymers

For optical display uses, such as organic light emitting devices (OLED's)

envisioned for PPP-NEt3+[19], the two most important physical properties for the

polymer are absorption and emission wavelengths and thermal stability. The absorption

and emission wavelengths will obviously control the color of the display device and

LED's operating under a high bias are limited in lifetime by thermal and electric field

induced degradations. Materials with low barriers to thermal degradation are of limited

use.

The solution absorbance and emission behavior of the newest PPP-NEt2[12] and

PPP-NEt3+[19] samples match the data reported for the initial polymer samples prepared

by Dr. Peter Balanda. Absorption spectra for the neutral polymer in THF (plot c), neutral

polymer in IM HC1 (plot b) and quatemized polymer in H20 (plot a) are represented on

the left half of the graph in Figure 2-16. Interestingly, a significant blue shifting of the

solution absorption maximum occurs from the neutral (4max = 350 nm) to quaternized

(rnax = 330 nm) polymer. In theory, the charges formed on the amine sites along the

backbone of the PPP polymer should repel other polymer chains and each other on the

same chain, stiffening each chain. This new state of the polymer should reduce steric

interactions and red shift the absorbance to lower energy. If this red shifting is occurring,

it is overcomefJy the additional effect of creating very specific point charges in space

along the backbone which in turn have their own effect on the absorption pushing it into

higher energy levels.

The solution emission results are plotted on the right half of Figure 2-16 and are

shown on a log scale to allow a comparison of the large differences in intensity of


I ... ..
,,.. .. ... W,. ,.. .':. :.:.
U 4-i..,. "." i :*B | *i ::







emission between the neutral polymer in THF (plot f), neutral polymer in IM HCI (plot

d), and the quaternized polymer in H20 (plot e). Each polymer has a brilliant blue

solution and thin film luminescence with an emission maximum wavelength of ca. 410

nm in THF and water. Intensity of luminescence increases 4 orders of magnitude in the

quaternized PPP-NEt3+[19] over the neutral polymer. This is attributed to the quenching

of the excited state by the lone pair of electrons on the nitrogen sites in the neutral

polymer. Quaternization prevents this quenching mechanism. Figure 2-17 shows the

emission results on a linear intensity scale normalized to 1 for the neutral polymer, PPP-

NEt2[12]. When the plot is viewed in this scaling, it is easily seen that the line shape of

emission is typical of photoluminescent polymers in solution with a broad peak and small

shoulder that tails into higher wavelength regions.

It was theorized that the PPPBP-NEt2[13] would have fewer side chain to

backbone interactions than PPP-NEt2[12] and thus a ,max at higher wavelength. Optical

absorbance and emission in solution was identical to that of the higher molecular weight

PPP-NEt2[12] samples. UV-Vis absorption measurements were taken on thin films cast

from THF of both PPPBP-NEt2[13] and PPP-NEt2[12]. The plots were nearly identical

with an absorption maximum just above 350 nm. If we assume that the oligomeric

PPPBP-NEt2[13] has reached a degree of polymerization such that its maximum

absorption wavelength has been achieved (typically this would be 12-15 rings or only a

degree of polymerization of 4 in this case), the similarity in thin film absorption data

indicates that the alkoxyamine side groups along the backbone of PPP-NEt2[12] are

disturbing the conjugated backbone planarity very little, allowing the conjugated

backbone to maintain a very rigid conformation.





43




2.5- 1

d
2- -- 0.1

o '
S-
t-4
S 1.5- 0.0




f O





0- 10

200 250 300 350 400 450 500 550 600
Wavelength


Figure 2-16. UV-Vis / Emission behavior of neutral and water soluble PPP-NEt.
a) PPP-NEt2[12] in THF: plots c and f
b) PPP-NEt2[12] in 1 M HCI: plots b and d
c) PPP-NEt3+[19] in HzO: plots a and e
Figure taken from Balanda, P.B.; Ramey, M.B.; Reynolds, J.R.
Macromolecules 1999, 32, 3970.


Thermal analysis by TGA (under nitrogen atmosphere) (Figure 2-18) indicated an

onset for decomposition over 300C for PPP-NEt2[12] and at ca. 230C for PPP-

NEts+[19] (with a small amount of water loss at lower temperatures). From the

perspective of device applications, the most important degradation event is the one which

occurs first. The first degradation event for both polymers was determined to be side

chain cleavage, including the loss of ethyl bromide for the quaternized sample. The


.' .. .. .. .










1.0


0.8





*- 0.4,
0.2-




0.0

350 400 450 500 550 600
Wavelength (nm)


Figure 2-17. Photoluminescent spectrum of PPP-NEt2[12] in THF with normalized and
linear emission scale.



fact that the thermal degradation of these alkoxy substituted PPP's is a relatively clean

process may provide a route to hydroxylated PPP's. Samples of PPP-NEt2[12] heated to

3000 for 10 min were no longer soluble in CHCI3 or THF, but did possess blue

photoluminescence when exposed to ultraviolet light. Treatment of PPP-NEt2[12] with

BBr3 (a reagent known for its ability to cleave aryl ethers) also resulted in a material

insoluble in CHCl3 or THF with the above mentioned emission characteristic.



Conclusions

An interesting water soluble poly(p-phenylene) (PPP-NEt3+[19]) has been

synthesized by a variety of modifications of Suzuki polymerization techniques. The use
..6 *





45

110(
(a)
90

U 70

^ .50-

"z 30

10

-10-*
0 200 400 600 800 100
Temperature


110 (b)
90 -

70


I)



-cO
-10 -.
0 do0 400 660 800 1000
Temperature
Figure 2-18. TGA thermograms for neutral and water soluble PPP-NEt under N2.
a) PPP-NEt2[12]
b) PPP-NEt3+[19]


of PdCl2(dppf) as catalyst has increased synthetic yield to the point whereby a relatively

high molecular weight polymer with low polydispersity can be made without the extra

steps of "cleaning" precipitated Pd out of the polymer. The PdCl2(dppf) catalyst was also

successful in allowing polymerization scale-up to the multi-gram level. For this system,

maximum chain growth is limited by the precipitation of longer polymer chains during

the coarse of the reaction.




i" t





46


Increasing the number of unsubstituted phenyl rings in the polymer backbone,

PPPBP-NEt2[13], lowers molecular weight due to precipitation of the polymer out of the

reaction prior to high conversions. Subsequent optical absorption data on thin film

castings of less substituted samples to the more substituted PPP-NEt2[12] helps support

the theory that the alkoxyamine side groups on PPP-NEt2[12] have minimal interactions

that affect backbone planarity.










































i Aq 'T4












CHAPTER 3
CATIONIC POLY(p-PHENYLENE-co-THIOPHENE)'s


Introduction

While poly(p-phenylene)'s such as PPP-NEt3+[19] are typically strong blue-

emitting polymers, it is desirable to have structurally similar materials with a range of

emission wavelengths. One approach to "tune" the emission wavelength of a polymer is

to chemically change the makeup of the backbone structure. By incorporation of more

electron rich moieties into the repeat unit structure, the highest occupied molecular

orbital (HOMO) to lowest occupied molecular orbital (LUMO) electronic bandgap is

lowered. Specifically, electron rich species raise the HOMO and have little effect on the

LUMO, thereby decreasing bandgap overall. As the bandgap is lowered, the energy

needed to excite an electron into the LUMO is reduced and therefore the energy

(wavelength) of light emitted upon relaxation will be of lower energy. For a more

complete description of light emission consult chapter 1 of this dissertation.

Inclusion of heterocycles, such as thiophene, furan, and pyrrole into co-polymers

with PPP attract much attention due to the substitution possibilities on phenylene rings

and the bandgap reduction due to a greater tendency towards planarity and electron

richness of the heterocycle. The original work to be discussed in this chapter will use the

incorporation of thiophene into the backbone of an alternating substituted phenylene-co-

thiophene polymer to create a water soluble polymer that emits at higher wavelengths

than the "parent" PPP-NEt3+[19] polymer discussed in Chapter 2 of this dissertation.







Early Synthetic Attempts

An early approach to incorporate thiophene units into a poly(p-phenylene-co-

thiophene) backbone was based on a poly(l,4-diketone) prepared by a Stetter reaction

that was treated with Lawesson's reagent to incorporate sulfur into the backbone (Figure

3-la).71 The harsh conditions required was a major flaw in this approach, as crosslinking

was promoted. Czerwinski et al. used a Grignard coupling between p-dibromobenzene

and 2,5-dibromothiophene in various feed ratios to incorporate thiophene and phenylene

units into the backbone (Figure 3-1b).72 Alternating copolymers containing arylene and

bithiophene repeat units have been synthesized via electrochemical polymerization of

1,4-di-2-thienylarylenes (Figure 3-1 ).73 The electrochemical polymerizations form

insoluble films on conductive substrates limiting polymer processing to the initial

deposition. Pelter et al. used zinc chloride to metalate the 5 and 5' positions of 1,4-di-(2-

thienyl)phenylene and reacted the intermediate with 1,4-dibromo-2,5-disubstituted

benzenes via a Grignard coupling (Figure 3-1d).74 The polymers could be doped by

ferric chloride or iodine to conductivities between 10-5 and 10-3 C-' cm .

Dr. Luping Yu and co-workers first report the synthesis of an alternating poly(p-

phenylene-co-thiophene) by a Stille coupling polymerization in 1993.75 The Stille

reaction offers much more flexibility in the selection. of monomers and reaction

conditions than many of the pathways shown in Figure 3-1. Figure 3-2 shows a general

polymerization scheme for a Stille type polymerization. In this case, 1,4-diiodo-2,5-

dialkoxybenzenes were reacted with 2,5-bis(tributylstannyl)thiophene. The polymers

were analyzed via gel permeation chromatography revealing a number average molecular






'. ; ... : .'.. ... :.....









+-00 -N N NaCN -


0' n


Lawesson's
Reagent


SBr Br + y Br Ni aca. SMg
2. Ni(acac)2


R

2 eq. M + Br Br Pd(0)

R


M = ZnCI, SnMe3

R = H, alkyl, alkoxy, functional group


Electrochemical
Oxidative Polymerization


R

S \

R


+ Br Pd(O) S


ZnCI R R

R = alkyl, alkoxy, nitro

Figure 3-1. Literature examples of phenylene-co-thiophene type polymers.



X-R-X + BusSn-R'-SnBus3 d(o) R-R'
n
X = I, Br, OS02CF3, COCI

R, R' = aromatic, vinyl, heterocyclic, etc.

Figure 3-2. General scheme for the'Stille polymerization.


(c)







n (d)


H 0


S .




50


weight of ca. 14,000 g mol-' versus polystyrene standards. This class of polymer

possesses a bandgap of ca. 2.4 eV (520 nm), falling between that of poly(p-phenylene),

3.0 eV (413 nm), and polythiophene, 2.1 eV (590 nm).76 An emission at 525 nm was

present in photoluminescence studies conducted in THF when the polymer solution was

excited with a wavelength of light corresponding to its absorption maximum when the

polymer solution was excited with a wavelength of light corresponding to its absorption

maximum.


Optimization of the Stille Coupling Polymerization

In order to maximize the efficacy of the Stille reaction for polymerizations, a

more detailed study by Yu et al. was conducted in 1995 to examine monomer, catalyst,

and solvent effects on the molecular weight of a variety of conjugated polymers.77 The

organohalides and triflates shown in Table 3-1 and the organotin monomers shown in

Table 3-2 were combined under a variety of conditions in the presence of palladium

catalysts. Polymer repeat unit structures are given in Figure 3-3.

Several general conclusions could be made from the polymers synthesized from

the different combinations of monomers and reaction conditions. Diiodo-substituted

monomers are more reactive than dibromo-substituted monomers. Dialkyl-substituted

phenylene monomers gave higher molecular weights than the more electron rich

dialkoxy-substituted phenylene monomers. The oxidative addition step in a palladium

catalyzed reaction is usually facilitated by electron withdrawing or less electron donating

groups. PPP type polymerizations were found to be poor in all cases with dimeric or

trimeric species formed. In general, the organotin monomer prefers to be electron rich

and the organohalide (or triflate) to be electron deficient.




: ".: .i ",:' t ""t, : .. .. '




51




Table 3-1. Structures of the organohalides and triflates for the Stille reactions.



R
1-8

Compound R X

1 OC8HI7
2 OC8HI7 Br
3 OC8HI7 OTf
i~ ~ ~ II. @ *ii iii i;liii








ii4 C CI








5 C81117 Br
-6 C8H17 OTf
7 OCIIH23 OTf
==== ; rl!i .. ..iiE I i ii



















S8 no substitution OTf
*Taken from Bao, Z.; akin, C.; Yu, J. Am. Chem. Soc. 1995, 117, 12426.


Table, 3-2. Structures of the organotin monomers for the Stille reactions.
upon! aIr susan suu















R
Me38n SnMe 3 R'3Sn -O SnR' 3

12 -14

Compound. R R$
12 OCH3 CH3
13 OCH3 n-49
14 OC7HI5 CH3
*Taken from Bao, Z.; Waikin, C.; Yu, L. J. Am. Chem. Soc. "1995, 117, 12426.



Typically 2 mol% catalyst was used as higher loadings of catalyst lowered

molecular weight. Adjustment of the 1: 1 organchalide to organtifioreactanit equivalent
i iir i i = ; i iiiiiillllii'liiiiiiiii i i iiiiiii == =
ii iiiliiiiiiiiiiii iii il~~ii iii =li i i iiii iiii~ i~ @ i ii 1= iiiiii ii~iiiiiiiii iii= = i i~ iiiiii! iii i ii ii iiii~iiiiii!iiiiiiiii ,= iiiiii i ~ iiiiiii iiiii ii iiii ili i iii iiiiiiiii! liiiili iiliiii i iili iiiiiiii
Ii .= iii~iiiiiiiiiii~ i~i ii =========" = ; iiiiiiiii i" liiiliiiiili~ i ii1 ii i 'iiiii iii iiiiiii iii
iiiiiiiliili iiii iiiii 1 1 iiliiliiiiii i "I i i i i ii iii ii i i i i L iiiii ii i ii iiii i i i i i i i= i i ii i ii iii~ iii iii = i = = iiiii iii iii iiiii iiiii ii= i iii i i i i i i i iii 1 ==i i i i i = = iiiii = iiii iii ii iii
.. i ii(1~ ii iiiiii
i i ililii ii iiii i ....................................... ... ;i;~ i iiiiii ii ii i i ii i i il i i i i i i i i i i l ii i i i i i i i i ii i i i i i i i i
= =;i iii iiiiiiii iiii iii iiiii i. c ;ii il ~ i lliiiiiiiiiiiiiiiiiiiiiii i i i ii.............== iiiiiiiiiiii i i ii~iiiiiiiii ii, ii i iliiiiiiiiiiiiiiii~l iii
iii iil i ii i i iii i ii iiiiiiiiiili~ i =il ii! iii il~ i ;iii i iiiii !i i iii ilii i ii i i iii iiii i ii il i iiii ii i iiili il lini i i i i i i ~ iiiiii i ii i iiiiii i iiii iiiiil i il i iiii i in
xiiiii riii i i a i =Ei~i i iiiiii= = i iii i = =iii iii i!= iiiiii iii l i i = !li i = == .. iii= = = .. iiiiiiiiiiiiii i ii ii~~lIi=iiili iil~ii~ iii~lii iiiiiiiiiiiiliiilii i ilIiIiillllii iii iiiiii iii ii i i iii i iiii iii iii~iilliiiiiiiiiiiiiiiii iii liiiiiii~ ~~iiiliiiiii= ii~
;;1;RJiiiiiii iiiiiiiiiiiiiii f l iiiiiiiiliiiiiiiii iiiiiliiiiiiiiii iiii iiiiiiiiiiiii iiiii iiiiliiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii iii.iiiili~i
'""; ; i iiiiiiiiiiiiiiiiii iiii ii iiiili iiiiii a iliiiiiiii i i ,i iiiiii!iiiiiiiiiii iiiiiiiii
i i iiiiiiiiiiiiiiiiii i i = = =i iiiiciiii =iiii ``
... .. .. ...... ... ................ ..... .. .= .... ... .. .... .... .. .. .... ........ .... =.... ............. ............... r = ........ ...... .......... .. .. .. .. .... ........ ;- I .. .. ........ ......... ........................ .....
:::::::::::::::::::::::: : :::::::::::::::::: :::: ::: : :::: : : : : :::::::::::::::::::::: : : : ::::::: :::::::::: :: : : : : ::::::: :::: :::::::: ::::::: ::::::::::: :::: ::::: : :::: ::: :: ::: : ::: ::::::::: :: : :: :::::::::: :::: ::::::::::::::::::: : ::::::: : ::::: .. ........ .:::::::: :::
!iiiiiii ii iii iii iii iliii~ iii = i i i~ iiii i ili i~ ii!! iiiii = i ii iii~ iii i~ ilii = =ii =i ii ili= ii i li !i i iiiiiiii ii ii i i !!!i = ii iiii !!iliii iii!!!!!!ii!iiiiii !!i ii
;;N-.~i. n ~;~ ;;;I ~


;s;;;'': o,


ii
I !
i~~li~i ....; ;Ea:;il

':':i;i;
;;; ,,,;0@,i..Pr !Ii;








rl,,, o ii iii s
ii il ..p "8I,
@: 8~












sa"NiOi.,r,,







ratio to account for reduction of the palladium (II) catalyst to the active palladium (0)

species by the organotin species increased molecular weights. The organotin compound

would be used in a 1.02 equivalent amount compared to 1.00 equivalent of organohalide.



R R


RR n
PPT PPV






Rn R R
n
PPP PPV

Figure 3-3. Representative polymer repeat units of Stille polymerizations.
R = CnH2zn+ or OCnH2n+i
Taken from Bao, Z.; Waikin, C.; Yu, L. J. Am. Chem. Soc. 1995, 117, 12426.



Ability of the solvent to both solubilize the coupled species and stabilize the

catalyst is of utmost importance in the Stille reaction and becomes an even more

important issue when addressing conjugated polymers and their inherent solubility

problems." Common solvents for the Stille reaction include THF, toluene, and DMF.

DMF is known to accelerate the palladium-catalyzed reactions by acting as a ligand to the

palladium center.7 In the case of the PPT polymers synthesized above, it was found that

DMF did accelerate the polymerization, however, the growing polymers were not

sufficiently soluble to remain in solution sufficiently long enough to achieve higher

molecular weights. THF was able to solubilize the polymer and stabilize the catalyst for

reaction times up to 7 days.



S ...: !
: '. :T ,.:.,,,r;.;,,,.:.".







Number average molecular weights of up to 22,000 g mol' were achieved for the

PPT polymers using 1.00 equivalent of 1,4-diiodo-2,5-dioctylbenzene, 1.02 equivalents

of 2,5-bis(tributylstannyl)thiophene, and 2 mol% PdC12(PPh3)2 catalyst in 80 oC DMF for

one week. Of all organotin monomers studied, the 2,5-bis(tributylstannyl)thiophene (see

Table 3-2) was the most reactive, as the electron donating property of the sulfur atom

may accelerate the transmetalation step which has been proposed to be the rate

determining step for palladium-catalyzed cross coupling reactions.80 An alternate tin

reagent not used in Yu's study is 2,5-bis(trimethylstannyl)thiophene, which is a more

"friendly" reagent in that it is a solid at room temperature allowing for purification by

recrystallization. The distillation techniques needed to purify 2,5-

bis(tributylstannyl)thiophene are difficult and workers may be exposed to alkyltin vapors,

which are very toxic. One drawback to the use of 2,5-bis(trimethylstannyl)thiophene is

the transfer of a methyl group during coupling instead of the desired thiophene group and

limiting chain lengths in polymerizations.

This methodology appeared attractive for coupling distannylated thiophene with

2,5-bis(3-[N,N-diethylamino]-l-oxapropyl)-1,4-diiodobenzene (DINEt)[see Chapter 2].

If successful, a neutral poly(p-phenylene-co-thiophene) with alkoxyamine side chains on

the phenylene units would be created that should become water soluble upon treatment

with ethyl bromide. The solution emission of this polymer should fall in the green to

yellow visible wavelength range by comparison to literature values. Using the insights

into the Stille coupling found by Yu and coworkers, and taking into account the specific

differences between the proposed system and the literature examples, a systematic

approach was designed to maximize the molecular weight of poly({2,5-bis[2-(N,N-




....... '. .... ." : h







diethylamino)- -oxapropyl]-1,4-phenylene }-alt-2,5-thienylene) (PPT-NEt2) which is

easily converted to the quaternary ammonium salt, poly(2,5-bis[2-(N,N,N-

triethylammonium)- -oxapropyl]- 1,4-phenylene-alt-2,5-thienylene I dibromide (PPT-

NEt3+). It was also desired to determine if a Suzuki type polymerization would work

using thiophene diboronic reagents. A Suzuki approach would allow for the use of much

less toxic boronic reagents than the tin reagents used in Stille couplings. The results and

discussion following will address these aspects in greater detail.


Results and Discussion


Monomer Syntheses and Suzuki Coupling Test Reactions

In order to effectively synthesize PPT-NEt3+ of high molecular weight via a Stille

or Suzuki polymerization, 2,5-bis(3-[N,N-diethylamino]- 1-oxapropyl)- 1,4-diiodobenzene

(DINEt) (Figure 2-7) and 2,5-bis(trimethylstannyl)thiophene (21) or 2,5-thiophene

diboronic acid (22) as co-monomers were selected. Literature precedent for Suzuki

polymerizations involving thiophene were not present, but success of this type of

polymerization was desired because the aryl tin reagents used in the Stille reaction are

somewhat less reactive as compared to the aryl boronic acids used in the Suzuki

coupling. A diiodobenzene monomer was chosen over a dibromo reagent due to its

higher reactivity in Pd coupling reactions. Particular attention was paid to the stringent

monomer purification requirements needed for complete conversion of functional groups.

The synthesis of 2,5-bis(trimethylstannyl)thiophene (21) by literature

methodology is outlined in Figure 3-4.81 Thiophene was treated with 2.05 equivalents of

n-butyllithium and refluxed in a hexane / TMEDA solution for 30 minutes, cooled to 0 C

in an ice bath, and quenched with 2.05 equivalents of trimethylstannyl chloride. After








stirring overnight, aqueous extraction, followed by removal of hexane under reduced

pressure revealed a slightly brown solid. The stannylated compound was distilled under

vacuum, and recrystallized twice from pentane to yield white crystals in 69% yield.

The corresponding Suzuki reagent, 2,5-thiophene diboronic acid (22) was

prepared by treating 2,5-dibromothiophene with 2.2 equivalents of Mg, followed by

quenching with an excess of dry trimethylborate. The reaction was stirred overnight and

IM HCI was added to protonate the di-acid and dissolve all magnesium salts. After an

aqueous/ Et20 extraction, the crude product was precipitated into IM HCI, collected, and

recrystallized from hot H20. A 40% yield of white crystals was recovered and dried in

vacuo at 100 oC for 3 hours. As is the case with boronic acids, purification and drying

were simplified by reacting the di-acid with neopentyl glycol in refluxing benzene in a

transesterification manner to produce the 2,5-thiophene diboronate ester (23) as white

crystals in 70% yield as outlined in Figure 3-5.



2.05 eq. n-BuLi
TMEDA LiLi 2.05 eq. Me3SnCI -oSn Sn,
0hexane RT, overnight
ref lux, 3 h. 2

69%

Figure 3-4. Synthesis of 2,5-bis(trimethylstannyl)thiophene.



Due to the lack of literature attempts at polymerizing a thiophene di-boronic acid

or ester, a test coupling procedure was carried out to determine if the reagent would

couple before degradation. A simple three component ring system was chosen instead of

test polymerizations for the study, since too many factors are present in polymerizations

: : ..
.,. .*.. ,

I: .: .. r., "::' ". "ijlj"." !i *!. ..
W
0 J i




56


that may deter the reaction. Figure 3-6 shows the general Suzuki coupling reaction

employed to check reaction parameters. A variety of conditions were used to couple

compound 23 and 4-bromotoluene. 4-bromotoluene was chosen over 4-iodotoluene

because of its lowered reactivity. In essence, if conditions are found to allow the

coupling to occur with bromo-reagents, iodo-reagents should perform better under the

same conditions and oftentimes the reactivity of bromo-compounds is sufficient for use in

Suzuki couplings eliminating the need for the more expensive iodine compounds.

Sodium bicarbonate (NaHCO3) and PdCl2(dppf) (1 mol%) were used as base and

catalyst, respectively, in all test reactions. Solvents were varied between THF, DMF, and

toluene, along with adjusting the reaction temperature from reflux to room temperature.

In all cases a mixed 5:1 ratio of the organic solvent to water was used to promote

formation of the more reactive boronate anion. To account for the high reactivity the

thiophene diboronate ester, reactions were conducted via one pot or the diboronate ester

was added slowly in a solution of solvent from an addition funnel.




Br Br 2.2 eq. Mg BrMg MgBr B(OCH3)3 H ~
t1 THF C r H* HO'- S OH
22
40%


HO OH
HO'B B 'OH
/S- Or-


+ excess K
A(


Figure 3-5. Synthesis of 2,5-thiophene dib


OH benzene 0 0
OH H20 BY
OH 'H\OY
23
70%

oronate ester. ''


.. ," .
.. **:;' .. -'. .


ii "." ,* .'" .':"'.:i. : .. i*,' .
i* ~" .; .....:. .i .
.p ,' ..i








B0B + -BrH3 PdCl2dppf H3C CH
or 10- NaHCO3
solvent, temp.,
23 method
24

Figure 3-6. Test coupling reaction of 2,5-thiophene diboronate ester and 4-bromotoluene.



Test reactions were monitored by thin layer chromatography to check for the

consumption of molecule 23 and 4-bromotoluene along with the appearance of new

compound spots. Reactions which displayed positive TLC results were worked up

isolating the organic products. Subsequently, the material was analyzed by gas

chromatography/mass spectrometry (GC/MS) to determine composition. Table 3-3 lists

the various reaction combinations and results.

Surprisingly, coupling to any significant level does not occur in THF. Typically,

even if THF proves to be a poor solvent for a Suzuki coupling, the reaction will proceed

to the 20-30% range. GC/MS peaks were assignable only to the starting materials with a

very small percent (<2%) of mono-substituted thiophene present upon slow addition of

the boronate ester. It was hypothesized that THF may be degrading the reactive thiophene

boronate ester. To help determine if this was the case, a small sample of compound 23

was placed in THF with catalyst and THF or DMF (and the correct ratio of water)

without 4-bromotoluene and heated to 50 oC for 3 hours. The "reactions" were stopped

and analyzed by GC/MS. Both revealed the peak assignable to compound 23 with no

degradation products evident. From these results, it is evident that THF and DMF do not

have any degradation effects on the boronate ester. The use of toluene as a higher boiling

solvent did not promote the reaction and GC/MS revealed higher levels of degradation





:,:"! .








products such as thiophene and its mono-boronate ester as a result of the higher

temperatures.



Table 3-3. GC/MS results of Suzuki coupling of 2,5-thiophene diboronate ester and 4-
bromotoluene.
Solvent Temp Catalyst Method Result

THF RT PdCl2dppf 1 pot SM


THF reflux PdClzdppf 1 pot SM + degradation


Toluene reflux PdCl2dppf 1 pot SM + large degradation


THF reflux PdCl2dppf dropwise low % mono


DMF RT PdCl2dppf 1 pot low % mono, SM


DMF 72 oC PdCl2dppf 1 pot Product 24,75%


DMF 72 oC PdCl2dppf dropwise Product 24 ,90%


DMF 72 oC Pd(OAc)2 dropwise Product 24,90%

RT = Room Temperature (-22 1C)
SM = Starting Materials (Compound 23 and 4-bromotoluene)
Mono = One tolyl unit coupled to thiophene


The coupling was successful in all cases in which DMF at elevated temperatures

was used. The ability of DMF to coordinate to the catalyst and increase catalytic activity

is believed to account for the success of using this solvent in the reaction. GC/MS

revealed good yields of product 24 for all DMF reactions at 72 OC, with excellent yields



..i"... ..








for cases in which the boronate ester was added dropwise. As an additional test, the less

reactive Pd(OAc)2 catalyst was used and yields for the reaction were as high as those for

the PdCl2(dppf). The ability of Pd(OAc)2 to be used in the coupling is important because

the catalyst is one of the least expensive Pd catalysts. For polymerizations using

compound 23, the test reactions indicate that using DMF at 72 oC with one pot or

dropwise addition of the boronate ester will be the best choice. These conditions will

provide the best possibility for polymerization success with only inherent polymerization

difficulties left to deter the reaction, such as solubility and complete conversion of

functional groups before hydrolysis of the boronate ester from the thiophene.


Neutral Polymer Syntheses

Initial polymerizations were conducted using the Stille coupling route because of

available guidelines in the literature for Stille couplings when used in thiophene

polymerizations. The Stille coupling polymerization used in the synthesis of poly({2,5-

bis[2-(N,N-diethylamino)-1 -oxapropyl]- 1,4-phenylene )-alt-2,5-thienylene) (PPT-NEt2)

is depicted in Figure 3-7. Gel permeation chromatography (GPC) and elemental analyses

for the subsequent experiments described below are presented in Tables 3-4 and 3-5,

respectively. It should be noted that the carbon analyses are significantly lower than what

is expected which may be due to the fact that these highly aromatic polymers are difficult

to combust and some carbonization may have occurred during the measurements. The

iodine elemental analyses provide a rough method for approximating the degrees of

polymerization. Not unexpectedly, attempts to synthesize PPT-NEt2 using the

dibromobenzene derivative, DBNEt, were unsuccessful with only low molecular weight

coupling products observed (results not shown).





60




N N


S S + I
DMF, 700C
21




DINEt
DINE Polymer Time Method
PPT-NEt2(48) [25] 48 h 1 pot
PPT-NEt2(96) [26] 96 h 1 pot
PPT-NEt2(240) [27] 240 h 1 pot
PPT-NEt2(96-drop) [28] 96 h dropwise

Figure 3-7. Stille coupling polymerization scheme for PPT-NEt2.



Reactions were conducted under varied conditions to determine the optimal

needed to achieve the highest molecular weight possible for PPT-NEt2. The first set of

reactions were carried out as one pot syntheses, where the stannylated compound,

DINEt, and DMF were mixed together and heated to 70 oC. PdCI2(PPh3)2 was then

added in one portion in a catalytic amount to the reaction flask. PPT-NEt2(48)[25] and

PPT-NEtz(96)[26] were synthesized with 48 and 96 hour reaction times followed by

precipitation into MeOH. During the polymerization, polymer was seen to precipitate out

and coat the reactor. PPT-NEt2(48)[25] was collected in75% yield with a Mn of 3,200

g mol',while PPT-NEtz(96)[26] was collected in 80% yield with a Mn of 4,100 g mol-

(GPC versus PS standards)(see Table 3-2). Polydispersities of 1.7 were found for both,

but with the extensive fractionation during purification this value is not indicative of the

initial polymerization. Doubling the reaction time lead to a modest improvements in both

a .... ....

S .. ." .. ... ..
.. .. ." .... ': ." .. .... .
.:i: ": ... ; :i







yield and M,, while increasing the reaction time to 10 days in PPT-NEtz(240)[27] led to

no appreciable molecular weight enhancement ( Mn of 4,200 g mol-').

Later experiments were fine tuned to account for the possible degradation of the

2,5-bis(trimethylstannyl)thiophene when exposed to elevated temperatures in the reaction

medium. PPT-NEt2(96-drop)[28] was synthesized by slow dropwise addition of 21 to a

solution of catalyst, DINEt, and DMF via an addition funnel over the course of 4 hours

and allowed to run for 96 hours. The reaction was precipitated into MeOH, the crude

polymer recovered by filtration, followed by extraction with MeOH and acetone for 24

hours each, and finally collected by extraction with chloroform (via Soxhlet extractor).




Table 3-4. Gel permeation chromatography results for Stille coupling of PPT-NEt2.
reaction reaction reaction M, MP M,,
polymer solvent type time kg mol-1 kg mol-1 kg mol-1 Mw/Mn
(hours)
PPT-NEt2 DMF Stille 48 3.2 4.3 5.2 1.70
(48)[25]
PPT-NEt2 DMF Stille 96 4.1 5.8 6.9 1.68
(96)[26]
PPT-NEt2 DMF Stille 240 4.2 5.4 7.2 1.71
(240)[27]
PPT-NEt2 DMF Stille 96 5.3 6.9 9.0 1.70
(96-drop)[28] (dropwise)
GPC results in THF vs. polystyrene standards.


The chloroform soluble fraction constituted an 84% yield and 'H and 3C NMR

analysis gave expected shift values with the proton peaks appearing as broad multiplets

without defined splitting for all polymeric materials recovered (see Figure 3-8). This

polymer exhibits a 'In, of 5,300 g mol' (GPC versus PS standards). This methodology




,..lI a. ,,,T' *: *SS..J ******...;., ;.. : .: i- .. ,





62




Table 3-5. Elemental Analysis results for PPT monomers and polymers.
Species %C %H %N %I %Br Anal. Calcd. for

Compound Theo. 29.32 4.92 CH2SSn2
21 Exp. 29.65 4.60

Compound Theo. 54.52 7.20 C4H22042S
23 Exp. 54.70 7.14 -

PPT-NEt2 Theo. 66.33 8.04 7.03 2.52 C22H32N202SIo.079
(48)[25] Exp. 65.23 7.84 6.65 2.50


PPT-NEtz Theo. 67.13 8.14 7.12 1.19 C22H32N202SIo.037
(96)[26]
(96)[26] Exp. 63.64 8.03 6.46 1.20 -


PPT-NEt2 Theo. 67.13 8.14 7.12 1.19 C22H32N202SIo.037
(240)[27] Exp. 63.99 7.99 6.60 1.22 -

PPT-NEt2 Theo. 67.38 8.17 7.15 0.97 C22H32N202SIo.030
(96-drop)[28] Exp. 63.99 8.02 6.51 0.98 -

C22H32N202SIo.037
PPT-NEt3+ Theo. 51.09 6.88 4.58 0.77 26.20 2 C2 037
P-NEt3 *2.0 C2H5Br
(96)[30]
Exp. 49.87 6.48 3.18 24.18

C22H32N202SI0.o030
Theo. 51.16 6.89 4.59 0.62 26.24 2 2HSB
PPT-NEt3+ "2.0 C2HsBr
(96-drop)[31]
] Exp. 49.73 6.52 3.29 23.62


PPT-NE2 Theo. 68.04 8.23 7.23 C22H32N202S
(Suz)[29]
Exp. 64.70 7.98 6.60 0.09



produced a polymer with the lowest percent of halogentated endgroups(weight %I = 0.98;

approximates a degree of polymerization = 27, corresponding to 54 rings) and highest



::: ... *** ::. .. .: .. : ::; ,, ,. : l l




63



molecular weight by GPC of all trials. Slow addition of the more reactive tin compound


allows for immediate coupling of the thiophene to DINEt. This limits the exposure of the


stannylated compound to the elevated temperatures and lowers the chance of destroying


the mass balance leading to end-capping of the polymer chains with thiophene or


completely de-stannylating the thiophene. This method led to the highest degree of


polymerization for the PPT's prepared.


rr
d
C
b
a


|^ LI


LII &LW 131 l III ID I I NI II II II 41 II I II pp


Figure 3-8. 'H and '3C NMR spectra of PPT-NEt2[28].


'. .:* ** **


"


* *







The next synthetic progression after confirmation that a base set of PPT-NEt2

polymers had been created was to try the Suzuki coupling methodology as outlined in

Figure 3-9. Compound 23 was added dropwise to a stirred solution of DINEt,

PdCl2(dpp), and NaHCO3 in a DMF / H20 solvent solution at 70 oC. After 3 days, the

reaction was precipitated into MeOH, the crude polymer recovered by filtration, followed

by extraction with MeOH and acetone for 24 hours each, and finally collected by

extraction with chloroform (via Soxhlet extractor). The material, PPT-NEt2(Suz)[29],

was recovered in 50% yield.





0
0 O / PdCl2dppf
0 DMF, 700C "N



H S H
HO / n=2-4
DINEt Hydrolysis of Boronate Groups PPT-NEt2(Suz)[29]
Low Molecular Weights Nc-




Figure 3-9. Synthesis of PPT-NEt2[29] via Suzuki coupling polymerization.



Elemental analysis of the polymer (see Table 3-5) initially indicated a possible

high molecular weight polymer with only 0.09 % by weight iodine found in the sample,

however, GPC trials indicated very low molecular weight oligomeric species. UV-Vis

absorption data showed a peak X. = 452 nm, some ten nanometers higher in wavelength

than the well analyzed materials from the Stille polymerization (see Physical Properties

4 1 0. ,







section). This evidence supports the conclusion that the growing chains in the Suzuki

reaction are being terminated by hydrolysis of the terminal boronate functionalities.

Lower molecular weight species and starting materials with iodine groups present were

removed by the extensive extractions performed, thus accounting for the low %I.

Unfortunately, the Suzuki reaction for thiophene boronates is not applicable to

polymerizations due to the ease of hydrolysis of the boronate. The Suzuki type reagents

and techniques would be good candidates for synthesis of smaller 3 to 4 ring compounds

as evidenced by the successful test reactions.


Polymer Ouaternization

Cationic, water soluble polymers are easily formed from the neutral PPT-NEt2 by

quaterization with bromoethane in THF as shown in Figure 3-10. The quaternized

polymer, PPT-NEt3+, was precipitated into acetone, collected, and dried at 50 oC under

vacuum. Table 3-5 shows the elemental analysis results for PPT-NEt3+(96)[30] and

PPT-NEt3+(96-drop)[31], which are the quaternized forms of PPT-NEt2(96)[26] and

PPT-NEt2(96-drop)[28], respectively. The resulting polymers are soluble in acidic

solution and pH = 7 water. The quaternization efficiency, as determined by 'H NMR

integration (comparison of the integral value of the terminal side chain protons,N-

CH2CH3*, to that of the O-CH2* protons [18:4 for 100% quaternization]), was on the

order of 80-90% per sample. This is also reflected in the elemental analysis [26.24% Br

by weight for complete alkylation compared to the 23.62% Br found for PPT-NEt3+(96-

drop)[31].







: "










N B0

Bromoethane
*07n "THF n
SRT/ 5d

N-\

PPT-NEt2 PPT-NEt3+

Figure 3-10. Quaternization of PPT-NEt2 to form PPT-NEt3+.



Physical Properties of PPT Type Polymers

Figure 3-11 shows the UV-Vis absorbance and photoluminescence spectra for

PPT-NEt2[28] in THF and PPT-NEt3+[31] in H20 (normalized for convenience). It is

interesting to note the dramatic shift in absorbance maximum between the neutral and

charged polymers. PPT-NEt2[28] exhibits a ,max at 460 nm with a corresponding molar

absorptivity of about 18,000 L mol'cm-', while PPT-NEt3+[31]'s Xa, is blue shifted 49

nm to 411 nm with a corresponding molar absorptivity of about 16,000 L mol'cm-'. The

blue shift of the 7t to I* transition for these polymers may be due to a solvatochromic

effect. Fine tuning of the Amax could be achieved by controlling the extent of

quaternization, as incomplete quatemization leads to a lower extent of hypsochromic

shift.

Solution photoluminescence experiments revealed peak emission wavelengths of

519 nm and 494 nm for PPT-NEt2[28] in THF and PPT-NEt3+[31] in H20, respectively.




67


The excitation wavelength corresponded to the ,max of each polymer's absorbance. The

spectra display the typical characteristics of conjugated polymers in solution with a

Stoke's shifted emission maximum and tailing broadly to higher wavelengths. Table 3-6

summarizes the optical properties for both the neutral and water soluble PPT polymers.


a bc d


/







vi


300 400 500 600 700
Wavelength (nm)


Figure 3-11. Normalized UV-Vis absorption and solution photoluminescence for PPT-
NEt type polymers.
a) PPT-NEt3+[31] UV-Vis absorption in H20.
b) PPT-NEt2[28] UV-Vis absorption in THF.
c) PPT-NEt3+[31] emission in H20.
d) PPT-NEt2[28] emission in THF.


It is interesting to note that the trend of increased absorbance and emission

intensity when moving from neutral to quaternized species for the PPP-NEt2 system was




..,E si'.E ., .


ai

E 0.8


0.6



E
.! 0.4

8

S0.2
0


0.0




S68


not observed for the PPT-NEtz polymers. In this case, quaternization led to a decrease in

the emission output of the polymer in solution. Initial data from collaboration work have

indicated that very little light is emitted from devices made from electrostatically

deposited thin solid films of PPT-NEt3+[31] excited by voltage application. Further

work is needed to explain this occurrence, since NMR did not reveal any unexpected

peaks for the polymer post quaternization.




Table 3-6. Summary of optical data for PPT-NEt type polymers.
Polymer Absorbance Film Emission Emission Color
max (nm) Color ,max (nm) (Solution)

PPT- 460 Red 519 Green
NEt2[28]


PPT- 411 Red 494 Green
NEt3+[31]



Thermal de-alkylation of the amine sites can occur if the polymer is exposed to

elevated temperatures, thus indicating a dynamic equilibrium at the amine sites. This de-

alkylation is evidenced in the TGA for PPT-NEt3+[31] shown in Figure 3-12 where an

initial degradation event starting at 200 oC is observed, followed closely by loss of the

triethylamine fragment. The initial weight loss event in the degradation of PPT-NEt2[28]

occurs at 250 C corresponding to the loss of this same triethylamine type fragment. Both

polymers have a final degradation occurring over 400 C, attributed to the breakdown of

the conjugated backbone and little residual mass remains.



.. .. : ..:











100-


80


60-
0-0
2 .........
S 40. -


20-


0

0 100 200 300 400 500 600 700 800
Temperature (oC)



Figure 3-12. TGA thermograms for neutral and water soluble PPT-NEt under N2.
a) -- PPT-NEt2[28]
b) ----- PPT-NEt3+[31]



Conclusions


A water soluble poly(p-phenylene-co-thiophene) (PPT-NEt3+[31]) has been

synthesized by a variety of modifications of Stille polymerization techniques. Maximum

molecular weight was achieved in DMF using PdCl2(PPh3)2 catalyst with slow addition

of the 2,5-bis(trimethylstannyl)thiophene reagent. Again, as in the case of the PPP-NEt2

system, the polymer does begin to precipitate from the reaction over the coarse of the

reaction, limiting the molecular weights. Polymerizations attempted in THF as solvent

did not produce polymeric materials. Unfortunately, the use of PPT-NEt3+[31] in

electroluminescent devices appears unlikely due to low light emission in such devices.

However, preliminary work has shown that the material may hold promise in

electrosttically deposited thin layer systems for control over refractive index properties.

... : .. .." : :

..





70



Adjustment of the number of PPT-NEt3+[31] layers deposited and thickness of the


layers dramatically changes and allows fine tuning of the refractive index of the


transparent "window" created by the device.


Investigations of test reactions using Suzuki coupling techniques were successful


using a 2,5 thiophene diboronate ester, however, the reagent was too susceptible to


hydrolysis to allow the synthesis of high molecular weight polymers as evidenced by a


lower absorption wavelength maximum than the Stille polymers. The 2,5 thiophene


diboronate ester is a viable alternative to more hazardous and toxic 2,5-


bis(trialkylstannyl)thiophene reagents for Pd coupling reactions to di-substitute thiophene


in the 2,5 positions.


4 .2


,;i
........
,
;;;


.:.... ..


.1*












CHAPTER 4
CATIONIC POLY(p-PHENYLENE-ETHYNYLENE)'s


Introduction


Early Synthetic Attempts

Poly(p-phenyleneethynylene)'s [PPE's] are a class of polymers that are composed

of alternating phenyl rings and triple bonds. They are structurally very similar to the

much studied polymer, poly(p-phenylenevinylene) [PPV], in which electroluminescense

from a conjugated polymer was first observed. PPE's did not receive the early attention

of PPV, but research efforts have increased as the luminescent and conducting properties

of PPE have been shown to be useful for explosive detection," molecular wires that

bridge nanogaps,83 and polarizers for liquid crystalline displays.

The first synthesis of PPE oligomers was reported in 1983 and consisted of

heating cuprous acetylide with diiodobenzene to a degree of polymerization of 10-12

(Figure 4-la).84 This type of approach, along with dehydrobromination of halogenated

PPV's (Figure 4-lb),85 and generation of PPE by electrochemical reduction of hexahalo-

p-xylene (Figure 4-1c)86, was unsuccessful in preparing well-defined systems without

defects and solubility of the resulting species was low. PPE's have also been synthesized

by ring-forming polycondensations, such as the reaction of acetylendicarboxylic amides

with hydrazine sulfate in polyphosphoric acid (PPA) followed by thermal cyclization of

the hydrazide groups (Figure 4-1d),87 and modifications to synthesize a wide variety of

rigid conjugated polyquinolines (Figure 4-Ie).88


71












Cu- -Cu + 1- -1


heat


PPE oligomers


S Br2
S CHCI3




n ---


200 300 C


Cu electr. -1.7 V, 24 h

0.1M BU4N'(CIO4)


0N
H2N NH2


+ H2N-NH2 'H2S04


PPA
-


N-N


0 1.0


di-m-cresyl phosphate
m-cresol
140 C


Figure 4-1. Early synthetic methodologies toward poly(p-phenyleneethynylene)'s [PPE].




Palladium (0) Coupling Reactions

Due to the limitations of the above routes, palladium cross coupling of terminal

alkynes to aromatic bromides or iodides in amine solvents is often the preferred

methodology to synthesize well-defined and soluble PPE's. This procedure is called the

.. ...'.:... .
'; I i
~1.1


PPE


PPE








Heck-Cassar-Sonogashira-Hagihara reaction and is one of the most frequently used

carbon-carbon bond forming processes in organic chemistry.8 Figure 4-2 outlines the

simple mono-coupling reaction scheme. Obviously, for polymer synthesis both reagents

are made difunctional and added to the reaction in precise stoichiometric amounts.






R Pd/ Cul R
+ 9 Amine


R = Alkyl, Aryl, X = Br, I
OH, Ether, Ester Y = Ester, Nitrile,
OR, NR3, Alkyl

Figure 4-2. General reaction scheme for the Heck-Cassar-Sonogashira-Hagihara
reaction.



Iodoaromatic compounds react faster and at lower temperatures than their

corresponding bromoaromatic analogs. Electron withdrawing groups on the halo-

aromatic compound increase the rate of the oxidative addition to the Pd(0). Elevated

temperatures necessary for the bromo reagents can lead to cross-linking and defect

formation. Choice of the amine solvent can have a dramatic effect on the reaction and it

has been found that diisopropylamine is an excellent choice for use with iodoarenes. PPE

polymerizations are conducted in concentrated solutions and amine solvents alone are not

good solvents for PPE's, therefore THF, ethyl ether, and toluene are commonly used

choices for co-solvents in the polymerizations.

The air stable, commercially available Pd(II) catalyst, PdCl2(PPh3)2, is often used

as tht source of Pd(0) in the coupling reaction and must be reduced to the active Pd(O)


"-.. ;i'.' .. ". ...... ....








species as outlined in Figure 4-3. Two molecules of a cuprated alkyne transmetallate the

Pd catalyst precursor and a symmetrical butadiyne is reductively eliminated, leaving an

active Pd(0) catalyst. PdCI2(PPh3)2 is used in 0.1-5 mol % amounts and varying amounts

of CuI are used as an alkynyl activator.90 Activation of the Pd(II) catalyst requires

consumption of the alkyne reagent which must be adjusted accordingly in

polymerizations to ensure a 1:1 stoichiometric balance with the haloaromatic compound.

A possible approach to solving the stoichiometric balance problem is the "pre-activation"

of the catalyst by addition of a monofunctional alkyne (such as phenylacetylene) to the

Pd(II) catalyst, thereby converting it to Pd(0). The catalyst solution could then be added

to the polymerization reagents and the diyne by-product of the catalyst activation would

not interfere with the stoichiometric balance.



R R
Amine / Cul C L2PdCl2
Ammonium Iodide -Cu2C12
R


L+ll L\
Pd Pd


Active Catalyst

_- R R


Reductive Elimination
Product

Figure 4-3. Activation of Pd(II) compound to active Pd(0) catalyst.








Dialkoxv-Polv(p-phenyleneethynylene)'s

The first soluble PPE derivatives were synthesized by Giesa with the

incorporation of long alkoxy groups to the rigid PPE backbone.91 Degrees of

polymerization on the order of 10-15 were achieved as a deeply colored solid was

recovered. Solubility was low and the deep coloration indicated extreme interchain

packing or some degree of crosslinking. Crosslinking can occur between internal or

terminal triple bonds in the polymer chain, lowering solubility and darkening the color of

the material and subsequently promoting inter-chain packing. An improved synthesis (see

Scheme 4-4) of similar PPE's was achieved by Moroni et al. with degrees of

polymerization of approximately 20.92 These workers did not take into account the

activation of the palladium catalyst, thus lowering molecular weights and introducing

diyne defects in the backbone.



OR' OR3
S= + x Pd cat.
amine
R20 RO Cul
X= Br or I


OR3 OR1 OR3

endgroup endgroup

R40 R20 R40

Figure 4-4. Synthesis of dialkoxy poly(p-phenyleneethynylene)'s via the Sonogashira
reaction.



Reduction of reaction temperatures to lower than 70 oC by Wrighton et al. in the

coupling of 2,5-diiodo-1,4-dialkoxybenzenes to 2,5-diethynyl-l,4-dialkoxybenzenes in a
C'i ."''. .







diisopropylamine/toluene mixture under PdCl2(PPh3)2/Cul catalysis led to polymers

without crosslinking and degrees of polymerization of up to 100.93 The same group

prepared interesting dialkoxy-substituted copolymers with 3-(dimethylamino)propyl and

7-carboxy-heptyl groups.94 Weder et al.95 utilized the branched solubilizing

ethylhexyloxy and linear octyloxy groups to prepare a polymer with a reported degree of

polymerization of 230, which were summarily reflected in the similar work of Swager

and coworkers who limited the molecular weight by the use of an imbalanced reaction

stoichiometry to ensure defined iodine endgroups.96

Other classes of PPE's have been created via the Sonogashira reaction that mix

di-alkoxy-substituted diiodides with different aromatic diynes. Examples include West's

use of 1,4-diethynylbenzene97 (Figure 4-5a) and Swager's use of al,4-

diethynylpentiptycene monomer to provide bulky chain spacing side-groups9 (Figure 4-

5b) or a bisamide compound better film forming properties (Figure 4-5c).99 Aryl- and

alkyl-substituted PPE's, which resemble a "true" unsubstituted PPE the most, were first

reported in 1995 by Bunz and Millen (Figure 4-5d).t10 A complete coverage of all PPE

type polymers synthesized by Pd(0) coupling methodologies would be impossible in this

dissertation, however, two excellent reviews by Giesa and Bunz on the subject matter are

available for reference.'10 Extensive work has also been accomplished in the field of

metal to ligand charge transfer between PPE's and coordinated metallic species.I02

The utility of the Sonogashira reaction for synthesizing well-defined PPE's, along

with its tolerance for functional groups, makes it applicable for incorporation of 2,5-

dialkoxyamine-phenylene units into a PPE backbone structure. These units can be

protonated with acidic treatment or quaternized with ethylbromide to provide an








interesting new class of polyelectrolyte. In general, such polymers should be yellow in

color and emit in the green region of the visible color spectrum. Due to the extensive

rigid-rod character of PPE's, special care will have to be taken with the resulting

materials to determine the effect different side chains on the second phenylene ring in the

repeat unit will have on the solubility of the initial neutral polymer and subsequently the

effect of bulky organic groups on the properties of the post-polymerization quaternized

polymer. If successful, this set of PPE polymers may provide polymers that emit in a

similar wavelength range as the poly(p-phenylene-co-thiophenes) [PPT's] discussed in

Chapter 3 and are more efficient emitters, which are capable of being cast as free

standing thin films.






C12H25 14 2 )9



OC12H25 OC4H29



(a) (b)



N(COaH7)2
C2oH21 O= C06H13 CH13



OC1oH21 jH=0i3 CeH13
N(CeH17)2

(c) (d)

Figure 4-5. Representative structures of synthetic modifications to poly(p-
phenyleneethynylene)'s.



Pr

.. ........ .
..".. .... ..:. T... .
... IEi : fi "" .i : :. ":" .





78



Results and Discussion


Monomer Syntheses

As illustrated in Figure 4-4, Sonogashira couplings require the usage of a di-

haloaromatic and a di-ethynylaromatic for an AA-BB type polymerization. Initial

monomer synthesis focused on the di-ethynyl reagent; the substitution of which will

greatly affect the solubility characteristics of the resulting polymer. Figure 4-6 outlines

the Williamson etherification procedure used to alkylate hydroquinone with

primary alkyl bromides.103 A suspension of powdered KOH was stirred in dry DMSO for

one hour followed by addition of hydroquinone and either hexyl- or nonyl-bromide. The

reactions were heated to 80 oC for 12 hours, cooled, poured into ice water, and extracted

with hexanes. The organic layer was subsequently washed with IM NaOH, water, brine,

OC6H13

4 eq. 5
OH B'Br KOH H13CO 32
+ or DMSO OCgH1i
H -- Br 80 0o (
HO

HigCgO 33

Compound % Yeld
32 83
33 79
Figure 4-6. Williamson etherification to synthesize various 1,4-dialkoxyphenylene's.



and dried over MgSO4. Removal of the solvent via reduced pressure evaporation led to

the isolation of reddish solids. The solids, 1,4-bis(hexyloxy)benzene (32) and 1,4-

bis(nonyloxy)benzene (33), were purified by recrystallization fromiethanol giving white

solids in 83 and 79 percent yields, respectively.



.: :....2
.: :. ::: ..:. : : E: E:I: : ...[[










OCeHi3
OCCH1H13
OCI I


SKO4,12 H13C60 34
H13C60 32
or AcOH / H20 / H2SO4 or
C9H70 C /12 h



H19C90 33 H19C90 35

Compound % Yield
34 79
35 85

Figure 4-7. Iodination of various 1,4-dialkoxybenzene's.



The 1,4-bis(alkoxy)benzenes (32 and 33) were iodinated under acidic conditions

using potassium periodate, iodine, and a mixed solvent system consisting of 90:7:3

HOAc/ H20/ HSO4 by volume with heating to yield 1,4-dialkoxy-2,5-diiodobenzenes

(34 and 35) as shown in Figure 4-7 in 79 and 85 percent yields as white crystals. The di-

iodides, 34 and 35, along with 1,4-diidobenzene were then subjected to a Sonogashira

coupling with (trimethylsilyl)acetylene in the presence of PdCl2(PPh3)2 and Cul catalysts

in an amine solvent. The 1,4-bis((trimethylsilyl)ethynyl) compounds[36-38] were isolated

via filtration of the reaction to remove amine salts and passed through a filter plug of

silica gel using toluene as eluent. After removal of the solvent, crude red solids were

obtained and recrystallized twice from ethanol to yield white crystals. The 1,4-

bis((trimethylsilyl)ethynyl) compounds were treated with either tetrabutylammonium

fluoride or aqueous KOH in THF to remove the TMS groups. The diethynyl compounds

(39-41) shown in Figure 4-8 were recovered in overall 70 to 82 percent yields based on



......... ./......








the appropriate starting di-iodide compound as light yellow or white crystals. Elemental

analysis results for compounds 39-41 are listed in Table 4-1.




OC8H13 OC6H13 OCgH13
I- TMS--TM-S H H

H13C60 34 H13C60 36 H13CSO 39
or C9H19 2.2 eq. or or
H SiH- TBAF or aq. KOH
I I TMS -- TMS H H
I PdCl2(PPh3)2 THF
H13CgO 35 Cul H1Cg9 37 H19C90 40
Et3N
or or or

-Q TMS -- TMS H-- = H
38 41

Compound % Yield
39 75
40 70
41 82


Figure 4-8. Synthesis of various 1,4-diethynylphenylene monomers.




The previously described di-iodide compound 2,5-bis(3-[NN-diethylamino]-l-

oxapropyl)-1,4-diiodobenzene (DINEt) was used in conjunction with the above di-

ethynyl compounds for Sonogashira polymerizations to provide a functional amine site to

be quaterized after polymerization (see Chapter 1). Synthesis of 2,5-bis(3-[N,N-

diethylamino]-1-oxapropyl)-1,4-dietihynylbenzene, produced by Pd(0) coupling of DINEt
i, b. a:..

with trimethylsilylacetylene and treatment with base, was attempted in order to have a

S companion reagent to DINEt, which upon Sonogashira polymerization with DINEt

would produce a PPE with every phenylene ring possessing alkoxyamine side chains.


.. .. .. L

S. ... .... ; ..
"..'-.* ..... .A .** : .. .: ." : : .. "i "'*:. ""i6 W ." :". !;:,,,"







Purification of the 2,5-bis(3-[N,N-diethylamino]-1-oxapropyl)-1,4-diethynylbenzene to a

level satisfactory for use in step growth polymerizations was hindered greatly by the


Table 4-1. Elemental analysis results for PPE monomers and polymers.
Species %C %H %N %I or Br Anal. Calcd.
for
Theo. 80.93 9.27 C22H3002
Compound
39 Exp. 81.20 9.15

Compound Theo. 81.89 10.32 C28H4202
40
40 Exp. 82.02 10.68

Compound Theo. 95.20 4.80 CoH
41 Exp. 95.60 4.60

PPE-NEtH Theo 71.78 7.26 5.98 1.05 C28H34N20210.04
PPE-NEtj/H
[51] Exp. 70.25 7.08 5.35 1.05

PPE-NEt2/ Theo. 75.64 9.20 4.41 0.67 C4o H58N204I. 10
OC6
[52] Exp. 72.10 7.89 4.01 0.67
PPE-NEtz/ Theo. 76.84 9.81 3.90 0.55 (1) C46H7oN2041.0o3
OC9(High)
[53] Exp. 76.11 9.79 3.47 0.55 ()
PPE-NEt2/ Theo. 76.98 9.83 3.90 0.37 (I) C46H7oN204lo.02
OC9(20)
[54] Exp. 75.66 9.64 3.41 0.37 (1)
C4QH7oN204
PPE-NEt3+/ Theo. 64.37 8.64 3.00 17.13 (Br) C46HN204
OC9(20)2 C2H5Br
OC9(20)
[56] Exp. 66.06 8.92 3.03 12.58 (Br) 35 C2HBr
-1.35 C2H5Br

extremely polar amine sites, which prevented column chromatography. Other means of

purification were unsuccessful in that distillation under reduced pressure resulted in the







h i.. .







cleavage of the triethylamine side groups and attempted recrystallization led to both

impurities and the desired compound to crystallized from the chosen solvents.

Taking into account the limitations imposed to purification by the polar amine

side groups of DINEt, it was desirous to have an alternate di-iodo monomer that

possesses the ability to form cationic amine sites, but does not contain amine sites from

the initial compound synthesis A route found in the literature used bromo-terminated

alkyl groups as side chains on benzene that were treated with triethylamine, imparting

water solubility with the resulting quatemized amine functionalities.04 Figure 4-9

outlines the synthesis of 2,5-bis(6-bromohexyl)-1,4-diiodobenzene which provides an

optional monomer to DINEt. It should be noted that this monomer does not have alkoxy,

but rather alkyl side chains and upon incorporation into a polymer backbone would raise

the energy of the 7 to 7I* transition compared to alkoxy containing PPE's.

Isolation of intermediate 43 was a challenging step in that that the presence of

unreacted starting material 42, which will prevent isolation of compound 44 in later steps,

must be removed by careful spinning band distillation under reduced pressure. The

distillation technique and equipment are dependent on user ability and several trials had

to be performed in order to maximize the separation ability of the apparatus. A rather

large spinning band column was used as 100g batches of compound 43 were typically

synthesized. Figure 4-10 shows the GC chromatogram of the reduced pressure

distillation of compound 43 using a simple vigreux column followed by a purification

using the spinning band technique. The initial simple distillation is not necessary for

purification, but was conducted to show the separation advantages of the spinning band

column. The small amount of 1,6-dimethoxyhexane present in the post- spinning band




:" .":` ." I "








distillation GC will not affect the next reaction and its presence is due to the fact that only

one major fraction was collected with priority on avoiding the higher boiling starting

material 42. Additional glassware pieces for the distillation apparatus have been

designed and allow for the collection of multiple fractions without disturbing the reduced

pressure of the column. Small changes in the pressure of the distillation during operation

will negate the separation benefits of the technique.




Br -Br NaOMe Br*OMe 1. Mg
42 MeOH / ether 43 2
reflux /2 days 70% Br -Br Ni (0) cat.


HBr
MeO OMe AcOH B r Br

44 45
62% 91%

45 Br Br
K104
H20,H2S04,
AcOH I 46
65%

Figure 4-9. Synthesis of 2,5-bis(6-bromohexyl)-1,4-diiodobenzene.



Pure compound 43 was reacted with Mg metal to form the Grignard reagent and is

added to a solution of 1,4-dibromobenzene and nickel catalyst to form compound 44,

which was isolated by simple vacuum distillation. The methoxy endroups were

converted to bromine by refluxing in a hydrogen bromide/acetic acid solution and

isolated as a colorless solid after recrystallization. This step was necessary as the

iodination conditions used to synthesize compound 46 were shown to cleave the methoxy

groups, giving a complex mixture of inseparable products. Compound 46 was collected



j 4A




84


in 65% yield as a white crystalline solid after recrystallization from methanol, based on

the amount of compound 45 used (overall 26 % yield based on starting compound 42).

Rehahn et al. demonstrated the technique of "protecting" the bromine groups by

etherification with phenol and reacting their 2,5-bis(6-phenyoxyhexyl)-1,4-

dibromobenzene with various phenylene boronic reagents to create poly(p-phenylene)'s.

The phenoxy end groups could be converted post-polymerization into iodo functionalities

by treatment with trimethyliodosilane followed by exposure to triethylamine to produce

charged, cationic amine sites along the backbone of the polymer (see Figure 4-11). These

PPP type polymers possessed significant solubility in water, but it should be noted that

more rigid PPE polyelectrolytes should inherently have more complex and lower

solubility behaviors in water.

The same methodology could be used to synthesize PPE type polymers with 6-

phenoxyhexyl sides that could undergo the above transformation to cationic amine sites.

The Williamson etherification of compound 46 with phenol is outlined in Figure 4-12.

Compound 50 could be used in Sonogashira type polymerizations to create interesting

PPE's, see Figure 4-13, which can be treated in the same manner as the PPP's in Figure

4-11 to achieve charged amine sites along the backbone. As the purpose of this body of

work is to focus on dialkoxy substituted PPE's, polymerizations utilizing 2,5-bis(6-

phenoxyhexyl)-l,4-diiodobenzene [50] were not conducted. However, the somewhat

difficult monomer synthesis has been fine tuned to allow the pursuit of these type of PPE

polymers by future workers.
.;. h. !
*, .:L.... ".



.:
: ** "* "* : ....


." :. ":
*.: ***"* .. ..,,: .. .:^,. ,:..tl .. ::.* i ':' ,i,^^i .,*^ ^, ..


































M"O..1NOMS


I I
4 6


MmOOr..roM.


8 10 12 min


I I I I
4 6 8 10 min
Figure 4-10. Gas chromatography analysis of purification of 6-bromohexylmethylether
(43) by vacuum distillation using (a) simple vigreux column and (b) spinning band
column.











" :..


B'~Br









CH12OPh

Br -Br

CsH12OPh


R
HO POH Suzuki
+ B -
HO ) OH Polymerizaton
R


R P6Hn2OPh

n
R CeH12OPh
47


R ,CH121
47 Trimethyliodosilane t-n

R C6H121
48


R C6H12NEt3s I-
Et3N f
ACN
R C6H12NEt3+ I-
49


Figure 4-11. Rehahn's route to cationic PPP's.


Phenol
Na*t-BuO

toluene / DMF I'
reflux, 16h


Figure 4-12. Williamson etherification to "protect" bromo endgroups.


C6H12OPh



CsH120Ph


R

+ -'

R


Sonogashira

Coupling


R CH1i2OPh


R CH1IOPh
R COH12OPh


R C6H12OPh
Trimethyliodosilane


R C6H12OPh


Et3N
ACN


R CgH12NEt3+ I



R C6Hi2NEt.+ I'


Figure 4-13. Envisioned application of Rehahn's strategy to PPE's.


ii"




87


Neutral Polymer Syntheses

The general Sonagashira polymerization is outlined in Figure 4-14. DINEt, di-

ethynyl compound, Cul co-catalyst, and Pd catalyst of choice, were stirred in a solution

of toluene and amine (triethylamine or diisopropylamine) with heating to 70 oC.

Temperatures above 70 oC are known to promote crosslinking in the PPE chains, along

with undesired diyne defects, and were therefore avoided. When Pd(II) catalysts are

employed, the amount of di-ethynyl compound should be adjusted to account for

reduction of the catalyst to Pd(0), as shown in Figure 4-3. Pd(0) catalysts, such as

Pd(PPh3)4, are effective for the coupling and do not need to be reduced before beginning

the catalytic cycle, but careful exclusion of 02 from the reaction must be conducted. For

the polymerizations in this study, diisopropylamine and Pd(PPh3)4 were used in all

couplings.




N N/


O R Pd(PPh3)4/ Cul 0 OR
Toluene
I + 1.02 eq. Toluene -
Diisopropylamine -
70 OC
R 700 RO
/ Rand



DINEt Polymer R

Monof l PPE-NEt2/H[51] H
Monofunctional PPE-NEt2/OC6[52] OCsH13
fEndapping Agent PPE-NEt/OC9(high) [53] OC9H19
for PPE-NEt2/QC(20) PPE-NEt2/OC9(20) [54] OCgHig

Figure 4-14. General synthesis for alkoxy-amine containing PPE's.



:,i...

.:,":i: ... ...... ..







Initial synthetic attempts at producing useful PPE's were performed with the

coupling of DINEt to 1,4-diethynylbenzene using toluene / diisopropylamine solvent

system (0.05M in DINEt) and 5 mol% Pd(PPh3)4 / Cul catalysts (PPE-NEt2/H[51]). A

slight excess of di-ethynyl compound is used (-1 mol %), even with an initial Pd(0)

catalyst, to account for unavoidable side reactions of the compound. After a reaction time

of 24 hours, a noticeable amount of material was precipitating from the reaction flask.

After cooling the reaction after 48 hours, the mixture was poured into cold ethanol and a

yellow solid recovered in nearly quantitative yield. This yellow material was insoluble in

hot chloroform, THF, or toluene. This result was not unexpected as PPE's are known for

their high susceptibility to packing when isolated as solids and subsequent poor

solubility. PPE-NEtz/H[51] was extracted with hot ethanol overnight, in an attempt to

remove catalyst residues. The polymer did appear to swell with solvent and was dried

overnight under vacuum. Elemental analysis was performed on the polymer sample to

help determine if crosslinking had occurred during polymerization. Carbon, hydrogen,

and nitrogen values are close to the predicted values for the polymer repeat unit structure.

Determination of molecular weight (via 'H NMR or GPC) was excluded by the

insolubility of the material. Elemental analysis of the material was consistent with the

proposed repeat unit structure (see Table 4-1).

Longer alkoxy groups were then used on the di-ethynyl reagent in hopes of

adding solubility in organic solvents to the neutral PPE's. Polymerization of compound

39, 1,4-diethynyl-2,5-bis(hexyloxy)benzene, with DINEt under the same conditions as

listed above for PPE-NEt2/H[51] was undertaken (PPE-NEt2/OC6[52]). Over the

coarse of 24 hours, the growing polymer remained in solution with no evidence of a




.., ': ".: ":::-. ""a .,




Full Text
122
polymer solution was precipitated into acetone, collected on a glass frit, washed
thoroughly with acetone, and dried in vacuo at 50 C overnight.
Poly{2,5-bis[2-(iV,/V,/V-triethylammonium)-l-oxapropyl]-l,4-phenylene-a/f-
2,5-thienylene} dibromide (PPT-NEt3+). *H NMR (300 MHz, D-,0) 7.22 (bm, 2 H),
6.90 (bm. 2 H), 3.96 (bm, 4 H), 3.12 (bm, 4 H), 2.70 (bm, 8 H), 0.55 (bm, 16.2 H) ppm.
UV-Vis (H2O) Xmax = 411 nm, log max = 4.20. PL (H2O with 411 nm excitation)
Xmax = 494 nm.
PPT-NEt3+(96)[30]. Anal, caled for C22H32N202SIo.o37*2.0 C2H5Br: C, 51.09;
H, 6.88; N, 4.58; Br, 26.20. Found: C, 49.87; H, 6.48; N, 3.18; Br, 24.18.
PPT-NEt3+(96-drop)[31]. Anal, caled for C22H32N202SIo.o30*2.0 C2H5Br: C,
51.16; H, 6.89; N, 4.59; Br, 26.24. Found: C, 49.73; H, 6.52; N, 3.29; Br, 23.62.
Chapter 4
General Procedure for Williamson Etherification of Hydroquinone. A
suspension of powdered KOH in 100 mL of DMSO was added to a dry 250 mL three
neck round bottom flask and stirred for 1 hour. Hydroquinone and the alkylbromide were
added in one portion under a steady stream of Ar. The reactions were stirred and heated
to 80 C for 12 hours. Upon cooling, the reaction mixture was poured into 300 mL of
H20. The aqueous mixture was extracted with hexane (3 x 100) and the combined
organics washed with 1M NaOH (300 mL x 1, 150 mL x 1, 50 mL x 1), H20 (300 mL x
1), and brine (300 mL x 1). After drying over MgS04, the solvent was removed by
reduced pressure evaporation.


98
Thermal de-protonation of the amine sites can occur if the polymer is exposed to
elevated temperatures, thus indicating a dynamic equilibrium at the amine sites. This de
protonation is evidenced in the TGA for PPE-NEt2H+/OC9(20)[55] shown in Figure 4-
19 where an initial degradation event starting at 188 C is observed (loss of HC1),
followed by a steady decline in weight (20 weight% remaining @ 522 C). The initial
weight loss event in the degradation of PPE-NEt2/OC9(20)[54] occurs slightly higher at
210 C followed by a steady decline in weight (20 weight% remaining @ 625 C). Both
polymers are completely degraded by a temperature of 700 C.
Temperature (C)
Figure 4-19. TGA thermograms for neutral and protonated PPE-OC9(20) under N2.
a) PPE-NEt2/OC9(20)[54] neutral
b) - PPE-NEt2H+/OC9(20)[55] protonated


active research areas of polymer chemistry. The importance of the early work on
polyacetylene was confirmed by the awarding of the 2000 Nobel Prize in Chemistry to
7
Figure 1-3. Band structure and density of states (DOS) diagram of a simple one
dimensional metal (polyacetylene) prior to and after a Peierls distortion.
a) Band structure prior
b) DOS prior
c) Band structure after Peierls distortion
d) DOS after Peierls distortion.
Eg is the bandgap, which for a semiconductor such as polyacetylene is twice the
activation energy for conduction.


19
synthesized with neutral alkoxy-triethylamine or alkylbromide side chains. These neutral
polymers can be analyzed using traditional techniques (GPC, NMR, etc.) and will possess
absorption and luminescence wavelengths that vary over the visible wavelength range
based on the electronic makeup of the backbone.
Alkoxy-triethylamine containing polymers were treated with bromoethane to form
the cationic dibromide salt of the original polymer. Likewise, the alkylbromide
containing polymers were treated with triethylamine to achieve the desired
polyelectrolytes. Molecular weight characteristics of the neutral polymer can be
approximately applied to the polyelectrolytes, since the treatments of the neutral polymer
do not break backbone linkages. Optical properties will be extensively investigated
focusing on the emission, absorption, and electrochromic responses from both the neutral
and water soluble polymers in solution and as prepared films


73
Heck-Cassar-Sonogashira-Hagihara reaction and is one of the most frequently used
89
carbon-carbon bond forming processes in organic chemistry. Figure 4-2 outlines the
simple mono-coupling reaction scheme. Obviously, for polymer synthesis both reagents
are made difunctional and added to the reaction in precise stoichiometric amounts.
R = Alkyl, Aryl, X = Br, I
OH, Ether, Ester Y = Ester, Nitrile,
OR, NR3, Alkyl
Figure 4-2. General reaction scheme for the Heck-Cassar-Sonogashira-Hagihara
reaction.
Iodoaromatic compounds react faster and at lower temperatures than their
corresponding bromoaromatic analogs. Electron withdrawing groups on the halo-
aromatic compound increase the rate of the oxidative addition to the Pd(0). Elevated
temperatures necessary for the bromo reagents can lead to cross-linking and defect
formation. Choice of the amine solvent can have a dramatic effect on the reaction and it
has been found that diisopropylamine is an excellent choice for use with iodoarenes. PPE
polymerizations are conducted in concentrated solutions and amine solvents alone are not
good solvents for PPEs, therefore THF, ethyl ether, and toluene are commonly used
choices for co-solvents in the polymerizations.
The air stable, commercially available Pd(II) catalyst, PdChCPPf^, is often used
as the source of Pd(0) in the coupling reaction and must be reduced to the active Pd(0)


52
ratio to account for reduction of the palladium (II) catalyst to the active palladium (0)
species by the organotin species increased molecular weights. The organotin compound
would be used in a 1.02 equivalent amount compared to 1.00 equivalent of organohalide.
R CnH2n+i or OCnH2n+l
Taken from Bao, Z.; Waikin, C.; Yu, L. J. Am. Chem. Soc. 1995,117, 12426.
Ability of the solvent to both solubilize the coupled species and stabilize the
catalyst is of utmost importance in the Stille reaction and becomes an even more
important issue when addressing conjugated polymers and their inherent solubility
problems.78 Common solvents for the Stille reaction include THF, toluene, and DMF.
DMF is known to accelerate the palladium-catalyzed reactions by acting as a ligand to the
palladium center.7'; In the case of the PPT polymers synthesized above, it was found that
DMF did accelerate the polymerization, however, the growing polymers were not
sufficiently soluble to remain in solution sufficiently long enough to achieve higher
molecular weights. THF was able to solubilize the polymer and stabilize the catalyst for
reaction times up to 7 days.


81
Purification of the 2,5-bis(3-[/V,yV-diethylamino]-l-oxapropyl)-l,4-diethynylbenzene to a
level satisfactory for use in step growth polymerizations was hindered greatly by the
Table 4-1. Elemental analysis results for PPE monomers and polymers.
Species
%C
%H
%N
%\ or Br
Anal. Caled.
for
Compound
Theo.
80.93
9.27
-
-
C22H30O2
39
Exp.
81.20
9.15
-
-
Compound
Theo.
81.89
10.32
-
-
C28H42O2
40
Exp.
82.02
10.68
-
-
Compound
Theo.
95.20
4.80
-
-
CioH
41
Exp.
95.60
4.60
-
-
PPE-NE2/H
Theo
71.78
7.26
5.98
1.05
C28H34N2O2I0.04
[51]
Exp.
70.25
7.08
5.35
1.05
PPE-NE2/
Theo.
75.64
9.20
4.41
0.67
C40 H58N2O4I0.10
OC6
[52]
Exp.
72.10
7.89
4.01
0.67
PPE-NEt-s/
OC9(High)
Theo.
76.84
9.81
3.90
0.55 (I)
C46H70N2O4I0.03
[53]
Exp.
76.11
9.79
3.47
0.55 (I)
PPE-NEtz/
Theo.
76.98
9.83
3.90
0.37 (I)
C46H70N2O4I0.02
OC9(20)
[54]
Exp.
75.66
9.64
3.41
0.37 (I)
PPE-NEt3+/
OC9(20)
Theo.
64.37
8.64
3.00
17.13 (Br)
C46H70N2O4
2 C2H5B1-
C46H70N2O4
1.35 C2H5Br
[56]
Exp.
66.06
8.92
3.03
12.58 (Br)
extremely polar amine sites, which prevented column chromatography. Other means of
purification were unsuccessful in that distillation under reduced pressure resulted in the


TABLE OF CONTENTS
page
ACKNOWLEDGMENTS iii
LIST OF TABLES vii
LIST OF FIGURES viii
ABSTRACT xi
INTRODUCTION 1
The Origination of Polymer Chemistry 1
Background and Theory of Conjugated Polymers 2
Bandgap: From Dienes to Extended Conjugation Systems 3
Luminescence: Photo- and Electro- 8
Conjugated Polymers for Electroactive Applications 11
Palladium(O) Coupling Reactions 13
General Catalytic Cycles and Mechanism 14
Conjugated Polyelectrolytes 17
Scope of the Dissertation 18
CATIONIC POLY(p-PHENYLENE) S 20
Introduction 20
Early Synthetic Attempts 20
Suzuki Couplings 22
Results and Discussion 25
Monomer and Model Compound Syntheses 25
Neutral Polymer Syntheses 30
Polymer Quatemization 39
Physical Properties of PPP Type Polymers 41
Conclusions 44
CATIONIC POLY(p-PHENYLENE-co-THIOPHENE)s 47
Introduction 47
Early Synthetic Attempts 48
Optimization of the Stille Coupling Polymerization 50
Results and Discussion 54


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 Philosoph'
lony R. Reynolds, Chair
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.
1^- l3
Kenneth B. 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.
Kirk S. Schanze
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.
gpjQ'dL
Daniel R. Talham f
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.
Anthony B. ttrennan
Associate Professor of Materials
Science and Engineering


79
pCgH^
Hi3C60 32
or
OCgHig
H19C90 33
KIO,
4 '2
AcOH / H20 / H2S04
70 C/12 h
OCgH^
Hi3C60 34
or
Compound % Yield
34 79
35 85
Figure 4-7. Iodination of various 1,4-dialkoxybenzenes.
The l,4-bis(alkoxy)benzenes (32 and 33) were iodinated under acidic conditions
using potassium periodate, iodine, and a mixed solvent system consisting of 90:7:3
HO Ac/ HiO/ H2S04by volume with heating to yield l,4-dialkoxy-2,5-diiodobenzenes
(34 and 35) as shown in Figure 4-7 in 79 and 85 percent yields as white crystals. The di
iodides, 34 and 35, along with 1,4-diidobenzene were then subjected to a Sonogashira
coupling with (trimethylsilyl)acetylene in the presence of PdCl2(PPh3)2 and Cul catalysts
in an amine solvent. The l,4-bis((trimethylsilyl)ethynyl) compounds[36-38] were isolated
via filtration of the reaction to remove amine salts and passed through a filter plug of
silica gel using toluene as eluent. After removal of the solvent, crude red solids were
obtained and recrystallized twice from ethanol to yield white crystals. The 1,4-
bis((trimethylsilyl)ethynyl) compounds were treated with either tetrabutylammonium
fluoride or aqueous KOH in THF to remove the TMS groups. The diethynyl compounds
(39-41) shown in Figure 4-8 were recovered in overall 70 to 82 percent yields based on


104
with a corresponding photoluminescent emission at 494 nm, placing the emission in the
blue-green region of visible light. The PPT polymers were slightly less thermally stable
than the PPP polymers, with initial degradation events under N2 occurring at 200 C.
Unfortunately, the use of PPT-NEt3+(96-drop)[31] in electroluminescent devices
appears unlikely as initial data from collaborative efforts have indicated very low
emission from thin layer devices. Unexpectedly, a promising application of the polymer
has arisen involving the use of PPT-NEt3+(96-drop)[31] in electrostatically deposited
thin layer systems for control over refractive index properties. Research is currently
ongoing with collaborators at MIT to uncover the exact nature and behavior of these
adjustable refractive index behaviors.
With the emission properties of the PPT polymers not meeting expectations, an
alternative blue-green emitting system was desired. Incorporation of ethynylene linkages
into the polymer backbone also lowers the energy of emission as compared to PPP.
Several experimental concepts were employed as the Sonogashira polymerization was
fine-tuned to produce the best polymer for the applications needed. The Sonogashira
reaction is an excellent polymerization route as the amine salt by-products that are
formed during the coarse of the reaction precipitate and help drive the reaction to
completion. The highly rigid nature of poly(/?-pheneyleneethynylene) makes solubility
issues crucial when designing the polymer. It was found that controlling molecular
weight via endcapping to a degree of polymerization of approximately 20 when reacting
l,4-diethynyl-2,5-bis(nonyloxy)benzene with DINEt, along with careful precipitation
and drying, was critical in isolation a soluble neutral polymer. A number average
molecular weight of 16,500 g/mol was estimated by 'H NMR, corresponding to a degree


124
58.0 mmol). Product was collected as a crude red/brown solid and purified by
recrystallization from ethanol yielding 20.20 g of a white, crystalline solid (79% yield).
mp. 52-53 C. H NMR (300 MHz, CDC13) 7.12 (s, 2 H), 3.92 (t, 4 H), 1.80 (m, 4 H),
1.35-1.50 (bm, 12 H), 0.91 (t, 6 H) ppm. 3C NMR (75 MHz, CDC13) 152.89, 122.87,
86.34, 70.42, 31.47, 29.14, 25.72, 22.59, 14.02 ppm. Anal. Caled for CigHzgC^: C,
40.75 ; H, 5.32. Found: C, 40.68; H, 5.31; N, 4.90. FAB-HRMS (M)+calculated for
C,8H2g02l2: 530.0179, Found 530.0178.
l,4-Bis(nonyIoxy)-2,5-diiodobenzene (35). Reagents: 1,4-
Bis(nonyloxy)benzene (9.14 g, 25.2 mmol), I2 (7.86 g, 30.3 mmol), and KIO4 (6.95 g,
30.3 mmol). Product was collected as a crude red/brown solid and purified by
recrystallization from ethanol yielding 13.13 g of a white, crystalline solid (85% yield).
mp. 52-53 C. H NMR (300 MHz, CDC13) 7.12 (s, 2 H), 3.93 (t, 4 H), 1.81 (m, 4 H),
1.29-1.50 (bm, 24 H), 0.89 (t, 6 H) ppm. 3C NMR (75 MHz, CDC13) 152.80, 122.73,
86.28, 70.33, 31.89, 29.52, 29.27, 29.14, 26.04, 22.70, 14.15 ppm. Anal. Caled for
C24H40O2I2: C, 46.90 ; H, 6.56. Found: C, 46.75; H, 6.83. FAB-HRMS (M)+calculated
for C24H40O2I2: 614.1118, Found 614.1116.
General Procedure for the Sonogashira coupling of trimethylsilylacetylene to
diiodobenzenes. The appropriate diiodobenzene, PdCl2(PPh3)2, and Cul were added to a
dry 150 mL side-arm flask under argon. Dry Et3N was added to the reaction via cannula
(~75 mL). The reaction mixture was stirred until reagents have dissolved and 3.0
equivalents of trimethylsilylacetylene are added in one portion. The reaction was heated
to 70 C and stirred overnight. After cooling, the reaction was filtered to remove


75
Dialkoxy-Polyfp-phenyleneethynyleneVs
The first soluble PPE derivatives were synthesized by Giesa with the
incorporation of long alkoxy groups to the rigid PPE backbone.91 Degrees of
polymerization on the order of 10-15 were achieved as a deeply colored solid was
recovered. Solubility was low and the deep coloration indicated extreme interchain
packing or some degree of crosslinking. Crosslinking can occur between internal or
terminal triple bonds in the polymer chain, lowering solubility and darkening the color of
the material and subsequently promoting inter-chain packing. An improved synthesis (see
Scheme 4-4) of similar PPEs was achieved by Moroni et al. with degrees of
polymerization of approximately 20. These workers did not take into account the
activation of the palladium catalyst, thus lowering molecular weights and introducing
diyne defects in the backbone.
OR1 OR3
Figure 4-4. Synthesis of dialkoxy poly(/?-phenyleneethynylene)s via the Sonogashira
reaction.
Reduction of reaction temperatures to lower than 70 C by Wrighton et al. in the
coupling of 2,5-diiodo-l,4-dialkoxybenzenes to 2,5-diethynyl-l,4-dialkoxybenzenes in a


84
in 65% yield as a white crystalline solid after recrystallization from methanol, based on
the amount of compound 45 used (overall 26 % yield based on starting compound 42).
Rehahn et al. demonstrated the technique of protecting the bromine groups by
etherification with phenol and reacting their 2,5-bis(6-phenyoxyhexyl)-l,4-
dibromobenzene with various phenylene boronic reagents to create poly(p-phenylene)s.
The phenoxy end groups could be converted post-polymerization into iodo functionalities
by treatment with tnmethyliodosilane followed by exposure to triethylamine to produce
charged, cationic amine sites along the backbone of the polymer (see Figure 4-11). These
PPP type polymers possessed significant solubility in water, but it should be noted that
more rigid PPE polyelectrolytes should inherently have more complex and lower
solubility behaviors in water.
The same methodology could be used to synthesize PPE type polymers with 6-
phenoxyhexyl sides that could undergo the above transformation to cationic amine sites.
The Williamson etherification of compound 46 with phenol is outlined in Figure 4-12.
Compound 50 could be used in Sonogashira type polymerizations to create interesting
PPEs, see Figure 4-13, which can be treated in the same manner as the PPPs in Figure
4-11 to achieve charged amine sites along the backbone. As the purpose of this body of
work is to focus on dialkoxy substituted PPEs, polymerizations utilizing 2,5-bis(6-
phenoxyhexyl)-l,4-diiodobenzene [50] were not conducted. However, the somewhat
difficult monomer synthesis has been fine tuned to allow the pursuit of these type of PPE
polymers by future workers.


59
for cases in which the boronate ester was added dropwise. As an additional test, the less
reactive Pd(OAc)2 catalyst was used and yields for the reaction were as high as those for
the PdCbidppf). The ability of Pd(OAc)2 to be used in the coupling is important because
the catalyst is one of the least expensive Pd catalysts. For polymerizations using
compound 23, the test reactions indicate that using DMF at 72 C with one pot or
dropwise addition of the boronate ester will be the best choice. These conditions will
provide the best possibility for polymerization success with only inherent polymerization
difficulties left to deter the reaction, such as solubility and complete conversion of
functional groups before hydrolysis of the boronate ester from the thiophene.
Neutral Polymer Syntheses
Initial polymerizations were conducted using the Stille coupling route because of
available guidelines in the literature for Stille couplings when used in thiophene
polymerizations The Stille coupling polymerization used in the synthesis of poly({2,5-
bis[2-(A,/V-diethylamino)-l-oxapropyl]-l,4-phenylene}-a/f-2,5-thienylene) (PPT-NE2)
is depicted in Figure 3-7. Gel permeation chromatography (GPC) and elemental analyses
for the subsequent experiments described below are presented in Tables 3-4 and 3-5,
respectively. It should be noted that the carbon analyses are significantly lower than what
is expected which may be due to the fact that these highly aromatic polymers are difficult
to combust and some carbonization may have occurred during the measurements. The
iodine elemental analyses provide a rough method for approximating the degrees of
polymerization. Not unexpectedly, attempts to synthesize PPT-NEt2 using the
dibromobenzene derivative, DBNEt, were unsuccessful with only low molecular weight
coupling products observed (results not shown).


36
Figure 2-12. Gel permeation chromatogram for PPP-NEt2(dppf)[12].
Table 2-1. Catalyst effect on the molecular weight properties of PPP-NEt2_polymers.
catalyst
reaction
solvent
yield
Calibration
method
K
kg mol'l
MP
kg mol'l
K
kg mol'l
Pd(OAc)2
THF
38%
PS
5.0
4.8
19.5
3.91
pppa
3.9
3.8
12.9
3.29
Pd(OAc)2
DMF
76%
PS
15.9
24.3
35.0
2.20
PPP
10.8
15.6
21.5
1.99
PdCl2(dppf)
THF
95%
PS
18.7
19.4
22.1
1.18
PPP
12.4
12.8
14.4
1.16
Pd(OAc)2
acetone
92%
PS
12.6
21.4
28.6
2.27
PPP
8.8
14.0
18.0
2.05
GPC results in CHCI3 vs. polystyrene standards.
Pd(OAc)2 data taken from Dr. Peter Balanda dissertation U. of Florida.
a
Universal calibration using values derived for PPP in THF.


106
complete set of conjugated polyelectrolytes with bandgaps that vary over lower visible
energy regions, such as addition of an alkoxy-amine substituted poly(p-
phenylenevinylene). Polymers tailored with specific energy absorptions and emissions
that could transfer energy to specific metal centers could easily be designed for sensing or
charge transfer studies. The guidelines future workers should follow are simple:
determine the properties needed, which type of conjugated polymer will meet the need,
and perform reactions!


65
section). This evidence supports the conclusion that the growing chains in the Suzuki
reaction are being terminated by hydrolysis of the terminal boronate functionalities.
Lower molecular weight species and starting materials with iodine groups present were
removed by the extensive extractions performed, thus accounting for the low %I.
Unfortunately, the Suzuki reaction for thiophene boronates is not applicable to
polymerizations due to the ease of hydrolysis of the boronate. The Suzuki type reagents
and techniques would be good candidates for synthesis of smaller 3 to 4 ring compounds
as evidenced by the successful test reactions.
Polymer Quatemization
Cationic, water soluble polymers are easily formed from the neutral PPT-NEt2 by
quatemization with bromoethane in THF as shown in Figure 3-10. The quatemized
polymer, PPT-NE3+, was precipitated into acetone, collected, and dried at 50 C under
vacuum. Table 3-5 shows the elemental analysis results for PPT-NEt3+(96)[30] and
PPT-NEt3+(96-drop)[31], which are the quatemized forms of PPT-NEt2(96)[26] and
PPT-NEt2(96-drop)[28], respectively. The resulting polymers are soluble in acidic
solution and pH = 7 water. The quatemization efficiency, as determined by H NMR
integration (comparison of the integral value of the terminal side chain protons,N-
CH2CH3*, to that of the O-CH?* protons [18:4 for 100% quatemization]), was on the
order of 80-90% per sample. This is also reflected in the elemental analysis [26.24% Br
by weight for complete alkylation compared to the 23.62% Br found for PPT-NEt3+(96-
drop)[31].


134
29. (a) Hatanaka, Y.; Hiyama, T. J. Org. Chem. 1988, 53, 918. (b) Hatanaka, Y.;
Hiyama, T. J. Org. Chem. 1989, 54, 268. (c) Hatanaka, Y.; Matsui, K.; Hiyama,
T. Tetrahedron Lett.. 1989, 30, 2403. (d) Hatanaka, Y.; Hiyama, T. J. Am. Chem
Soc.. 1990, 772,7793. (e) Review: Hatanaka, Y.; Hiyama, T. Synlett 1991,845.
30. (a) Suzuki, A. Acc. Chem. Res. 1982, 15, 178. (b) Suzuki, A. Pure Appl. Chem.
1985, 57, 1749. (c) Miyaura, N.; Suzuki, A. J. Synth. Org. Chem. Jpn. 1988, 46,
848. (d) Miyaura, N.; Suzuki, A. J. Synth. Org. Chem. Jpn. 1993, 51, 1043. (e)
Suzuki, A. Pure Appl. Chem. 1991,63,419. (f) Suzuki, A. Pure Appl. Chem.
1994, 66, 213.
31. (a) Heck, R.F. J. Am. Chem. Soc. 1968, 90, 5518. (b) Recent Review: Crisp,
G.T. Chem. Soc. Rev. 1998, 27, 427.
32. Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron Lett. 1975, 4467.
33. General Reviews: (a) Kochi, J.K. Organometallic Mechanisms and Catalysis',
Academic: New York, 1978. (b) Heck, R.F. Palladium Reagents in Organic
Syntheses', Academic: New York, 1985. (c) Hartley, F.R.; Patai, S. The
Chemistry of Metal-Carbon Bond', Wiley: New York, 1985; Vol. 3. (d)
McQuillin, F.J.; Parker, D.G.; Stephenson, G.R. Transition Metal
Organomet allies for Organic Syjithesis', Cambridge University Press: Cambridge,
1991. (e) Tamao, K. Comprehensive Organic Synthesis; Trost, B.M., Fleming,
I., Pattenden, G., Eds.; Pergammon: New York, 1991; Vol. 3, p 435. (f)
Hegedus, L.S. Organometallics in Organic Synthesis', Schlosser, M., Ed.;
Willey: New York, 1994; p 383.
34. (a) Forster, S.; Schmidt, M. Adv. Poly. Sci. 1995,726,51. (b) Schmitz, K.S.
Macroions in Solution and Colloid Suspension', VCH Publishers: New York,
1993. (c) MacCallum, J.R.; Vincent, C.A.. Polymer Electrolyte Reviews',
Elsevier: London: 1987.
35. Steven, M.J.; Kremer, K. J. Chem. Phys. 1995,103, 1669.
36. Resting, R.E. Synthetic Polymeric Membranes, 2nd. Ed.; Wiley: New York,
1985.
37. (a) Ried, W.; Freitag, D. Naturwiss. 1966, 53, 305. (b) Dineen, J.M.; Volpe,
A.A. Am. Chem. Soc., Poly. Div., Polym. Prepr. 1978, 19, 34. (c) Krigbaum,
W.R.; Krause, K.J. J. Polym. Sci., Polym. Chem. Ed. 1978, 76, 3151. (d)
Dineen, J.M.; Howell, E.E.; Volpe, A.A. J. Polym. Sci., Polym. Chem. Ed. 1982,
23, 1259. (e) Ballard, D.G.H.; Courtis, A.; Shirley, I.M.; Taylor, S.C. J. Chem.
Soc., Chem. Commun. 1983, 954. (0 Mukai, K.; Teshirogi, T.; Kuramoto, N.;
Kitamura, T. J. Polym. Sci., Poly. Chem. Ed. 1985, 23, 1259. (g) Brdas, J.L.
J.Chem. Phys. 1985, 82, 3808.


Ill
MeOFLTbO twice to give white microcrystalline product which was dried in vacuo over
CaS04. Yield 8.89 g [38 %], mp 76-78C. [H NMR (300 MHz, CDC13) ppm. 7.12 (s, 2
H), 4.05 (t, 7 = 5.4 Hz, 4 H), 2.75 (t, 7 = 5.8 Hz, 4 H), 2.34 (s, 12 H) ppm. 13C NMR
(75.4 MHz, CDCI3) 150.55, 119.37, 111.61,69.39, 58.18, 46.02 ppm. Anal, caled for
Ci4H22N202Br2: C, 41.00; H, 5.41; N, 6.83. Found: C, 41.13; H, 5.44; N, 6.71.
l,4-Diphenyl-2,5-bis(3-[N,Af-diethylamino]-l-oxapropyl)phenylene (10). A
150 mL side arm vacuum flask with magnetic stir bar was flame dried under vacuum and
backfilled with Ar gas. 50 mL of DMF and 10 mL of H2O were added and sparged with
Ar for 30 min. DINEt (0.80 g, 1.4 mmol), phenylboronic acid (0.40 g, 3.3 mmol), and
NaHCCri ( 84.0 g, 14.0 mmol) were added and allowed to dissolve. PdChidppf) (0.030
g, 0.04 mmol) was added in one portion and the reaction stirred with heating to 50 C for
12 hours. After cooling, 50 mL of Et2 and H2O each were added and the organic
fraction collected. The aqueous layer was extracted with Et20 (2 x 50 mL) and the
combined organics were washed with 1M NaOH (3 x 50 mL), H2O (3 x 50 mL), and
finally with brine (1 x 100 mL). The organics were dried over MgS04, and the solvent
removed under vacuum revealing a yellowish white solid. The product was dissolved in
THF and filtered through a plug of silica gel to remove catalyst contamination. After
removal of solvent, a white solid was recovered. Yield 0.449 g [68 %]. }H NMR (300
MHz, CDCI3) ppm. 7.58 (d, 7 = 6.6 Hz, 4 H), 7.39 (t, 7 = 7.1 Hz, 4 H), 7.32 (d, 7 = 7.1
Hz, 2 H), 6.98 (s, 2 H), 3.97 (t, 7 = 6.0 Hz, 4 H), 2.75 (t, 7 = 6.0 Hz, 4 H), 2.50 (q, 7 = 7.1
Hz, 8 H), 0.95 (t, 7 = 7.1 Hz, 12 H) ppm. 13C NMR (75.4 MHz, CDCI3) 129.55, 127.90,
126.91, 116.63,68.74,52.06,47.81, 12.03 ppm. Anal, caled for C30H40N2O2: C, 78.21;


23
polymerization.30 51 A-B polymerization of 4-bromo-2,5-dialkylbenzeneboronic acids
and AA/BB polymerization of l,4-dibromo-2,5-dialkylbenzeneboronic acids was
performed (Figure 2-2). Chain lengths of 100 rings were achieved leading to
processable, substituted PPPs.52
The success of the Suzuki reaction with its use of less electropositive boron
reagents, high yield couplings, and tolerance for mixed aqueous / organic solvent systems
opened the door to a variety of functionalized PPPs hitherto unreachable. One of the
most interesting sub-fields to arise from this methodology was the synthesis of
conjugated, rigid polyelectrolytes. The first rod-like polyelectrolytes were reported in the
early 1980s and were based upon poly(l,4-phenylenebenzobisoxazole) and poly(l,4-
CT
phenylenebenzobisthiazole). Careful incorporation of anionic or cationic functionality
into a PPP yields a material that possesses the beneficial properties of a conjugated
polymer with the aqueous solubility and processability of a polyelectrolyte. The
environmental utility of aqueous processing techniques applicable to polyelectrolytes is a
potential advantage of these materials for use in an industrial setting. Carboxylate
(Figure 2-3a,b),54 sulfonate (Figure 2-3c),35 and sulfonatopropoxy groups (Figure 2-3d)36
have been used to create anionic PPP polyelectrolytes.
Figure 2-2. Suzuki coupling approaches to substituted poly(/>-phenylene).


136
54. (a) Wallow, T. I.; Novak, B. M. J. Am. Chem. Soc. 1991,113, 7411. (b) Rau,
I.U.; Rehahn, M. Makromol. Chem. Phys. 1993, 194, 2225. (c) Rau, I.U.;
Rehahn, M. Polymer 1993, 34, 2889. (c) Rau, I.U.; Rehahn, M. Acta
Polymerica 1994, 45, 3.
55. Rulkens, R.; Schulze, M.; Wegner, G. Macromol. Rapid Commun. 1994, 15, 669.
56. (a) Child, A.D.; Reynolds, J.R. Macromolecules 1994, 27, 1975. (b) Kim, S.;
Jackiw, J.; Robinson, E.; Schanze, K. S.; Reynolds, J. R.; Baur, J.; Rubner, M. F.;
Boils, D. Macromolecules 1998, 31, 964.
57. Brodowski, G.; Horvath, A.; Ballauff, M.; Rehahn, M. Macromolecules 1996, 29,
6962.
58. (a) Balanda, P.B.; Ph.D. Dissertation, University of Florida 1997. (b) Balanda,
P.B.; Ramey, M.B.; Reynolds, J.R. Macromolecules 1999, 32, 3970.
59. Baur, J.; Kim, S.; Balanda, P. B.; Reynolds, J. R.; Rubner, M. F. Adv.
Mater.,1998, 10, 1452.
60. Chang, S.C.; Bharathan, J.; Helgeson, R.; Wudl, F.; Yang, Y.; Ramey, M.B.;
Reynolds, J.R. Appl. Phys. Lett., 1998, 73, 2561.
61. Hong, L.; Powell, D. R.; Hayashi, R. K.; West, R. Macromolecules 1998, 31, 52.
62. Peng, Z.; Gharavi, A. R.; Yu, L. J. Am. Chem. Soc. 1997, 119, 4622.
63. Coutts, I. G. C.; Goldschmid, H. R.; Musgrave, O. C. J. Chem. Soc.(C) 1970,
488.
64. Rehahn, M.; Schluter, A.-D.; Wegner, G. Makromol. Chem. 1990,191, 1991.
65. Harrison, B.S.; Ramey, M.B.; Reynolds, J.R.; Schanze, K.S. J. Am. Chem. Soc.
2000, 722, 8561.
66. Moreno-Maas, M.; Prez, M.; Pleixats, R. J. Org. Chem. 1996, 61, 2346.
67. Kowitz, C.; Wegner, G. Tetrahedron 1997, 53, 15553.
68. Hayahi, T.; Konishi, M.; Kobori, Y.; Kumada, M.; Higuchi, T.; Hirotsu, K. J.
Am. Chem. Soc. 1984, 106, 158.
69. Steffen, W.L.; Palenik, G. J. J. Inorg. Chem. 1976, 5, 2432.
70. Ishiyama, T.; Murata, M.; Miyaura, N. J. Org. Chem. 1995, 60, 7508.
71. Power, K.L.; Vries, T.R.; Havinga, E.E.; Meijer, E.W.; Wynberg, H. J. Chem.
Soc., Chem. Commun. 1988, 1432.


39
and transesterification with neopentyl glycol. Both attempts were unsuccessful, possibly
caused by an interaction of the amine groups to the trimethyl borate hindering formation
of the new phenyl-boron bond. Grignard and lithiation procedures were effective as
evidenced by a substantial amount of dehalogenated material in the crude isolated
material. Future work could explore using a palladium catalyzed reaction between di-
halogenated phenylenes and diboron pinacol ester (see Figure 2-14) that has been shown
to effectively produce boronic reagents for Suzuki reactions70 as an alternative route to
the desired compound 18.
Polymer Quatemization
Quatemization of the amine sites followed preparation of the neutral polymers.
Synthesis of poly[2,5-bis(2-{N, A.A-triethylammoniumJ-l-oxapropyO-l^-phenylene-tf/f-
1,4-phenylene] dibromide (PPP-NEt3+[19]) is accomplished by heating the neutral
polymer in a DMSO / THF solution with bromoethane for 3 days (Figure 2-15). 'H-
NMR indicates that a high degree of the amine sites are quatemized (-90%). Elemental
analysis for bromine content also reflects 90% quatemization (see Table 2-2). The beauty
of synthesizing the neutral polymer first is in the ease of traditional polymer analyses that
can be performed. Analysis of charged polyelectrolytes can be a rigorous and difficult
undertaking,especially with GPC due to aggregation and charge interaction with the
column material. Assuming the methods used to quatemize the amine sites are gentle
enough not to break bonds along the PPP backbone or cleave side chains, molecular
weight data corresponding to the neutral polymer should be a good reflection of the
molecular weight of the water soluble version. PPP-NEt.v-[19] displayed excellent
solubility in both acidic and neutral aqueous media. Solutions were stable over the time


45
Figure 2-18. TGA thermograms for neutral and water soluble PPP-NEt under N2.
a) PPP-NEt2[12]
b) PPP-NEt3+[19]
of PdCl2(dppf) as catalyst has increased synthetic yield to the point whereby a relatively
high molecular weight polymer with low polydispersity can be made without the extra
steps of cleaning precipitated Pd out of the polymer. The PdCl2(dppf) catalyst was also
successful in allowing polymerization scale-up to the multi-gram level. For this system,
maximum chain growth is limited by the precipitation of longer polymer chains during
the coarse of the reaction.



PAGE 1

6<17+(6,6 2) 9$5,$%/( %$1'*$3 &21-8*$7(' 32/<(/(&752/<7(6 9,$ 0(7$/ &$7$/<=(' &5266&283/,1* 5($&7,216 %\ 0,&+$(/ %5,$1 5$0(< $ ',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

7KLV GLVVHUWDWLRQ LV GHGLFDWHG WR -DPHV % DQG -HZHOO 4 5DPH\ DQG 5DOSK DQG *HRUJLD 4XDOOV ZKRVH OLIHORQJ ZRUN HQFRXUDJHPHQW DQG ORYH KDYH PDGH WKH FRQVWUXFWLRQ RI WKLV GLVVHUWDWLRQ SRVVLEOH

PAGE 3

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

PAGE 4

IDQ ZRUNRXW SDUWQHU DQG VFLHQWLILF FRQVXOWDQW DQG &'XERLV ZKR LV RQH HQWHUWDLQLQJ &DMXQ EXW UHVSHFWIXO DQG FRPSHWHQW ODE FRZRUNHU ,9

PAGE 5

7$%/( 2) &217(176 SDJH $&.12:/('*0(176 LLL /,67 2) 7$%/(6 YLL /,67 2) ),*85(6 YLLL $%675$&7 [L ,1752'8&7,21 7KH 2ULJLQDWLRQ RI 3RO\PHU &KHPLVWU\ %DFNJURXQG DQG 7KHRU\ RI &RQMXJDWHG 3RO\PHUV %DQGJDS )URP 'LHQHV WR ([WHQGHG &RQMXJDWLRQ 6\VWHPV /XPLQHVFHQFH 3KRWR DQG (OHFWUR &RQMXJDWHG 3RO\PHUV IRU (OHFWURDFWLYH $SSOLFDWLRQV 3DOODGLXP2f &RXSOLQJ 5HDFWLRQV *HQHUDO &DWDO\WLF &\FOHV DQG 0HFKDQLVP &RQMXJDWHG 3RO\HOHFWURO\WHV 6FRSH RI WKH 'LVVHUWDWLRQ &$7,21,& 32/
PAGE 6

0RQRPHU 6\QWKHVHV DQG 6X]XNL &RXSOLQJ 7HVW 5HDFWLRQV 1HXWUDO 3RO\PHU 6\QWKHVHV 3RO\PHU 4XDWHPL]DWLRQ 3K\VLFDO 3URSHUWLHV RI 337 7\SH 3RO\PHUV &RQFOXVLRQV &$7,21,& 32/
PAGE 7

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f W\SH SRO\PHUV YLL

PAGE 8

/,67 2) ),*85(6 )LJXUH 3DJH 6WUXFWXUHV RI SRO\"SKHQ\OHQHWHUHSKWKDODPLGHf f SRO\EHQ]RELVWKLD]ROHf f DQG SRO\SSKHQ\OHQHf f $SSOLFDWLRQ RI )URVWfV FLUFOH WR LOOXVWUDWH WKH HQHUJLHV RI PROHFXODU RUELWDOV ZLWKLQ F\FOLF V\VWHPV %DQG VWUXFWXUH DQG GHQVLW\ RI VWDWHV '26f GLDJUDP RI D VLPSOH RQH GLPHQVLRQDO PHWDO SRO\DFHW\OHQHf SULRU WR DQG DIWHU D 3HLHUOV GLVWRUWLRQ *HRPHWULFDO UHOD[DWLRQ RI D 339 FKDLQ LQ UHVSRQVH WR SKRWR RU HOHFWR H[FLWDWLRQ 3RODURQ ELSRODURQ DQG VLQJOHW H[FLWRQ HQHUJ\ OHYHOV LQ D QRQGHJHQHUDWH JURXQG VWDWH SRO\PHU (OHFWURQLF WUDQVLWLRQV LQ D FRQMXJDWHG SRO\PHU LH 339f VKRZLQJ ERWK VLQJOHW DQG WULSOHW VWDWHV *HQHUDO FDWDO\WLF F\FOH IRU 3Gf FURVV FRXSOLQJ UHDFWLRQV 6\QWKHWLF PHWKRGV WR SRO\SSKHQ\OHQHf 6X]XNL FRXSOLQJ DSSURDFKHV WR VXEVWLWXWHG SRO\"SKHQ\OHQHf $QLRQLF SRO\"SKHQ\OHQHfnV UHSRUWHG LQ WKH OLWHUDWXUH &DWLRQLF SRO\SSKHQ\OHQHfnV UHSRUWHG LQ WKH OLWHUDWXUH 5 KH[\Of &RQYHUVLRQ RI GLPHWKR[\EHQ]HQH WR GLLRGRK\GURTXLQRQH %URPLQDWLRQ RI K\GURTXLQRQH LQ WKH SRVLWLRQV :LOOLDPVRQ HWKHULILFDWLRQ RI ',+4 RU '%+4 6\QWKHVLV RI GLERURQLF SKHQ\OHQH UHDJHQWV IRU XVH LQ 6X]XNL FRXSOLQJV 6\QWKHVLV RI QHXWUDO DQG FDWLRQLF 333 PRGHO FRPSRXQGV YLLL

PAGE 9

6X]XNL SRO\PHUL]DWLRQV IRU QHXWUDO DONR[\DPLQH FRQWDLQLQJ 333fV &O3G&O ERQG DQJOH IRU 3G&/&GSSHf 3G&ALGSSSf DQG 3G&/&GSSIf FDWDO\VWV *HO SHUPHDWLRQ FKURPDWRJUDP IRU 3331(WGSSIf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fWKLRSKHQH 6\QWKHVLV RI WKLRSKHQH GLERURQDWH HVWHU 7HVW FRXSOLQJ UHDFWLRQ RI WKLRSKHQH GLERURQDWH HVWHU DQG EURPRWROXHQH 6WLOOH FRXSOLQJ SRO\PHUL]DWLRQ VFKHPH IRU 3371(W n+ DQG O& 105 VSHFWUD RI 3371(W>@ 6\QWKHVLV RI 3371(W>@ YLD 6X]XNL FRXSOLQJ SRO\PHUL]DWLRQ 4XDWHPL]DWLRQ RI 3371(W WR IRUP 3371(W 1RUPDOL]HG 899LV DEVRUSWLRQ DQG VROXWLRQ SKRWROXPLQHVFHQFH IRU 3371(W W\SH SRO\PHUV 7*$ WKHUPRJUDPV IRU QHXWUDO DQG ZDWHU VROXEOH 3371(W XQGHU 1 (DUO\ V\QWKHWLF PHWKRGRORJLHV WRZDUG SRO\"SKHQ\OHQHHWK\Q\OHQHffV >33(@ *HQHUDO UHDFWLRQ VFKHPH IRU WKH +HFN&DVVDU6RQRJDVKLUD+DJLKDUD UHDFWLRQ $FWLYDWLRQ RI 3G,,f FRPSRXQG WR DFWLYH 3Gf FDWDO\VW ,;

PAGE 10

6\QWKHVLV RI GLDONR[\ SRO\SSKHQ\OHQHHWK\Q\OHQHffV YLD WKH 6RQRJDVKLUD UHDFWLRQ 5HSUHVHQWDWLYH VWUXFWXUHV RI V\QWKHWLF PRGLILFDWLRQV WR SRO\" SKHQ\OHQHHWK\Q\OHQHffV :LOOLDPVRQ HWKHULILFDWLRQ WR V\QWKHVL]H YDULRXV GLDONR[\SKHQ\OHQHfV ,RGLQDWLRQ RI YDULRXV GLDONR[\EHQ]HQHfV 6\QWKHVLV RI YDULRXV GLHWK\Q\OSKHQ\OHQH PRQRPHUV 6\QWKHVLV RI ELVEURPRKH[\OfOGLLRGREHQ]HQH *DV FKURPDWRJUDSK\ DQDO\VLV RI SXULILFDWLRQ RI EURPRKH[\OPHWK\OHWKHU f E\ YDFXXP GLVWLOODWLRQ XVLQJ Df VLPSOH YLJUHX[ FROXPQ DQG Ef VSLQQLQJ EDQG FROXPQ 5HKDKQfV URXWH WR FDWLRQLF 333fV :LOOLDPVRQ HWKHULILFDWLRQ WR fSURWHFWf EURPR HQGJURXSV (QYLVLRQHG DSSOLFDWLRQ RI 5HKDKQfV VWUDWHJ\ WR 33(fV *HQHUDO V\QWKHVLV IRU DONR[\DPLQH FRQWDLQLQJ 33(fV f+ DQG & 105 RI 33(1(W2&f>@ LQ &'& ([SDQVLRQ RI WKH DURPDWLF UHJLRQ RI WKH f+ 105 RI 33(1(W2&f>@ LQ &'& &RQYHUVLRQ RI 33(1(W2&f>@ WR FDWLRQLF SRO\HOHFWURO\WHV 1RUPDOL]HG 899LV DEVRUSWLRQ DQG VROXWLRQ SKRWROXPLQHVFHQFH IRU 33(2&f W\SH SRO\PHUV 7*$ WKHUPRJUDPV IRU QHXWUDO DQG SURWRQDWHG 33(2&f XQGHU 1 [

PAGE 11

$EVWUDFW RI 'LVVHUWDWLRQ 3UHVHQWHG WR WKH *UDGXDWH 6FKRRO RI WKH 8QLYHUVLW\ RI )ORULGD LQ 3DUWLDO )XOILOOPHQW RI WKH 5HTXLUHPHQWV IRU WKH 'HJUHH RI 'RFWRU RI 3KLORVRSK\ 6<17+(6,6 2) 9$5,$%/( %$1'*$3 &21-8*$7(' 32/<(/(&752/<7(6 9,$ 0(7$/ &$7$/<=(' &5266&283/,1* 5($&7,216 %\ 0LFKDHO %ULDQ 5DPH\ 0D\ &KDLUPDQ 'U -RKQ 5 5H\QROGV 0DMRU 'HSDUWPHQW &KHPLVWU\ 0HWDO FDWDO\]HG FRXSOLQJ UHDFWLRQV VXFK DV WKH 6WLOOH 6X]XNL DQG 6RQDJDVKLUD +HFNf KDYH EHFRPH XVHIXO WRROV IRU WKH RUJDQLF FKHPLVW RYHU WKH SDVW WZR GHFDGHV IRU WKH IRUPDWLRQ RI FDUERQFDUERQ ERQGV 7ROHUDQFH RI IXQFWLRQDO JURXSV UHDVRQDEOH UHDFWLRQ WHPSHUDWXUHV DQG KLJK \LHOGV KDYH DOORZHG WKHVH WHFKQLTXHV WR EH DSSOLHG WR WKH V\QWKHVLV RI FRQMXJDWHG SRO\PHUV 7KHVH V\QWKHVHV RIIHU DFFHVV WR D ZLGH YDULHW\ RI FRQMXJDWHG EDFNERQH VWUXFWXUHV WKDW KDYH SUHYLRXVO\ EHHQ GLIILFXOW WR UHDFK XVLQJ WUDGLWLRQDO SRO\PHUL]DWLRQ WHFKQLTXHV 3RO\SSKHQ\OHQHf >333@ SRO\"SKHQ\OHQHF!WKLRSKHQHf >337@ DQG SRO\S SKHQ\OHQHFRHWK\Q\OHQHf >33(@ HOHFWURO\WHV KDYH EHHQ SUHSDUHG E\ XVLQJ RQH RI WKH DIRUHPHQWLRQHG FRXSOLQJ WHFKQLTXHV $ PHWKRGRORJ\ ZDV DSSOLHG ZKHUHE\ FKDUJH QHXWUDO SRO\PHUV ZHUH ILUVW V\QWKHVL]HG DQG WKHQ FRQYHUWHG WR WKH FRUUHVSRQGLQJ FDWLRQLF SRO\HOHFWURO\WH 7KLV fSUHSRO\PHUf WHFKQLTXH DOORZV IRU VWXGLHV FRPSDULQJ QHXWUDO SRO\PHU SURSHUWLHV LH DEVRUSWLRQ OXPLQHVFHQFH VROXELOLW\f WR WKRVH RI WKH [L

PAGE 12

SRO\HOHFWURO\WH 6LJQLILFDQW FKDQJHV LQ WKH SRO\PHUVf YLVLEOH DEVRUSWLRQ DQG HPLVVLRQ f ZDYHOHQJWKV RFFXU EHWZHHQ WKH GLIIHULQJ EDFNERQH VWUXFWXUHV 7KH SRO\HOHFWURO\WHVf RSWLFDO WUDQVLWLRQV DUH VKLIWHG WR KLJKHU HQHUJLHV EOXHVKLIWHGf YHUVXV WKH DEVRUSWLRQ DQG HPLVVLRQ RI WKH QHXWUDO YHUVLRQ ZLWKLQ WKH VDPH SRO\PHU EDFNERQH W\SH 7KH HIIHFWV RI KDORJHQDWLRQ RI WKH PRQRPHU VROYHQW W\SH DQG SDOODGLXP FDWDO\VW RQ WKH PROHFXODU ZHLJKW ZHUH GHWHUPLQHG IRU HDFK VHW RI QHXWUDO SRO\PHUV E\ PRQLWRULQJ FKDLQ H[WHQVLRQ E\ JHO SHUPHDWLRQ FKURPDWRJUDSK\ ,Q WKH FDVH RI WKH 333 GHULYDWLYHV LW ZDV IRXQG WKDW WKH 6X]XNL SRO\PHUL]DWLRQ SURFHHGV WKH IDVWHVW WR PD[LPXP PROHFXODU ZHLJKW LQ D '0) DTXHRXV PHGLD XVLQJ 3G&OGSSIf FDWDO\VW ZLWK GLLRGLQDWHG PRQRPHU 3RO\PHUL]DWLRQV XVLQJ GLEURPLQDWHG PRQRPHUV UHDFKHG VLPLODU PROHFXODU ZHLJKW YDOXHV EXW RQO\ DIWHU ORQJHU UHDFWLRQ WLPHV 3RO\PHU FKDLQ JURZWK LQ WKLV V\VWHP ZDV OLPLWHG E\ WKH SUHFLSLWDWLRQ RI SRO\PHU IURP WKH UHDFWLRQ VROXWLRQ DQG QRW WKH UHDFWLYLW\ RI WKH KDORJHQDWHG PRQRPHU 337 SRO\PHUV V\QWKHVL]HG XVLQJ WKH 6WLOOH UHDFWLRQ SURFHHGHG WR KLJKHVW PROHFXODU ZHLJKW YDOXHV LQ DQK\GURXV '0) XVLQJ 3G&O33Kf FDWDO\VW DQG GLLRGLQDWHG PRQRPHU 7ULHWK\ODPLQH 7+) VROYHQW V\VWHPV XVLQJ 3G&O33Kf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

PAGE 13

&+$37(5 ,1752'8&7,21 7KH 2ULJLQDWLRQ RI 3RO\PHU &KHPLVWU\ 2YHU WKH SDVW RU VR \HDUV SRO\PHU VFLHQFH DQG FKHPLVWU\ KDYH HYROYHG IURP HDUO\ UXEEHU DQG %DNHOLWH W\SH FKHPLVWULHV WR H[WHQVLYHO\ FKDUDFWHUL]HG DQG FRPPHUFLDOL]HG PDWHULDOV /RRNLQJ EDFN RQ WKH HDUO\ HYROXWLRQ RI WKLV EUDQFK RI VFLHQFH WRGD\fV REVHUYHU ZRXOG ILQG YLJRURXV GHEDWHV RQ WKH H[DFW QDWXUH RI SRO\PHUV ZHUH WKH\ OLQHDU SRO\PHUV KHOG WRJHWKHU LQ ORQJ FKDLQV E\ FRYDOHQW ERQGV RU PHUHO\ fDJJORPHUDWLRQVf RI VPDOOHU PROHFXOHV KHOG WRJHWKHU E\ LRQLF IRUFHV" 7RGD\ ZH NQRZ WKDW WKH\ DUH LQGHHG EDVHG RQ WKH ILUVW SULQFLSOH DV SURSRVHG DQG GHIHQGHG E\ 6WDXGLQJHU 1HFHVVLW\ SURYHG WR EH WKH PRWKHU RI LQYHQWLRQ DV WKH QHHG WR UHSODFH QDWXUDO LWHPV VXFK DV VLON 1\ORQ f DQG UXEEHU FLV SRO\EXWDGLHQHf LPSRUWHG IURP IRUHLJQ FRXQWULHV WR WKH 8QLWHG 6WDWHV ZDV RI XWPRVW LPSRUWDQFH GXULQJ :RUOG :DU ,, DV WKH FRQIOLFW WKUHDWHQHG WR FXW RII VXSSOLHV )URP WKHVH EHJLQQLQJV WKH VWXG\ DQG HYHU\GD\ XVH RI PDQPDGH SRO\PHUV KDV H[SORGHG SRVVLEO\ EHVW H[HPSOLILHG E\ WKH ZKLVSHULQJ RI WKH OLQH f-XVW RQH ZRUG SODVWLFVf LQ WKH +ROO\ZRRG PRYLH 7KH *UDGXDWHf 6\QWKHWLF SRO\PHUV DUH D PDMRU FRUQHUVWRQH RI WKH HQWLUH LQGXVWULDO FKHPLFDO ZRUOG DQG EDVLF UHVHDUFK RQ WKHVH PDWHULDOV KDV HQDEOHG VFLHQWLVWV WR XQGHUVWDQG QDWXUDO SRO\PHUV VXFK DV SURWHLQV RQ GHHSHU OHYHOV WKDQ HYHU EHIRUH :LWK VXFK EURDG DQG VZHHSLQJ DSSOLFDWLRQV DQG YDULDWLRQV WKURXJKRXW SRO\PHU FKHPLVWU\ D FRPSOHWH RYHUYLHZ RI WKH VFLHQFH ZRXOG EH LPSRVVLEOH WKHUHIRUH D fJXLGHG WRXUf ZLOO EH SUHVHQWHG KHUHLQ RXWOLQLQJ

PAGE 14

WKH EXLOGXS RI UHSHDW XQLWV DQG SURSHUWLHV ZLWKLQ FRQMXJDWHG SRO\PHU V\VWHPV PDWHULDOV ZLWK DOWHUQDWLQJ VLQJOH DQG GRXEOHWULSOH ERQGVf 7KHVH SRO\PHUV KDYH H[FLWLQJ QHZ DSSOLFDWLRQV IRU RSWLFDO GLVSOD\ PDUNHWV ZKLFK FRXOG QHYHU KDYH EHHQ HQYLVLRQHG GXULQJ WKH HDUO\ GD\V RI WKH VFLHQFH %DFNJURXQG DQG 7KHRU\ RI &RQMXJDWHG 3RO\PHUV 2QH RI WKH VLPSOHVW RUJDQLF PROHFXOHV LV WKH WZR FDUERQ PROHFXOH HWKHQH &+&+ ZKLFK H[LVWV DV D JDV XQGHU VWDQGDUG WHPSHUDWXUH DQG SUHVVXUH 3RO\PHUL]DWLRQ RI WKH PROHFXOH OHDGV WR ORQJ FKDLQV RI FRYDOHQWO\ ERXQG WZR FDUERQ XQLWV &+&+f WHUPHG SRO\HWK\OHQH $V WKH QXPEHU RI FRYDOHQW ERQGV LQFUHDVHV WKH PDWHULDO PRYHV WKURXJK OLTXLG UHSHDWVf ZD[\ UHSHDWVf EULWWOH SODVWLF UHSHDWVf DQG WRXJK SODVWLF UHSHDWVf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

PAGE 15

)XQFWLRQDOL]HG SRO\PHUV FDSDEOH RI K\GURJHQ ERQGLQJ LQWHUDFWLRQV FDQ KDYH ORZHUHG VROXELOLW\ DV ZHOO 3RO\PHUV WKDW IRUP H[WHQGHG ULEERQOLNH VWUXFWXUHV LQ VROXWLRQ UDWKHU WKDQ D UDQGRP FRLO FRQIRUPDWLRQ DUH WHUPHG ULJLGURG SRO\PHUV 6XFK SRO\PHUV DUH H[HPSOLILHG E\ SRO\"SKHQ\OHQHWHUHSKWKDODPLGHf SRO\EHQ]RELVWKLD]ROHf DQG SRO\SSKHQ\OHQHf VKRZQ LQ )LJXUH 3RO\PHU PDLQWDLQV LWV ULJLGURG QDWXUH E\ K\GURJHQ ERQGLQJ EHWZHHQ FKDLQV DQG SRO\PHUV DQG PDLQWDLQ WKH VDPH QDWXUH E\ EHLQJ HQWLUHO\ FRQMXJDWHG 7KH FRQMXJDWHG SRO\PHUV KDYH WKH XQLTXH SURSHUW\ RI EHLQJ HOHFWURDFWLYH PHDQLQJ WKH\ KDYH GLHOHFWULF DQG VSHFWUDO SURSHUWLHV VXFK DV OXPLQHVFHQFHf WKDW GHSHQG RQ DSSOLHG YROWDJHV %HFDXVH RI WKH HOHFWURDFWLYH QDWXUH RI FRQMXJDWHG SRO\PHUV WKH\ KDYH EHFRPH D PDMRU IRFXV RI UHVHDUFK RYHU WKH ODVW RU VR \HDUV ,W LV HDV\ IRU RQH WR IRFXV VROHO\ RQ WKH RSWLFDO SURSHUWLHV GXH WR WKH YLVXDO QDWXUH RI KXPDQV KRZHYHU LW LV LPSRUWDQW QRW WR IRUJHW PHFKDQLFDO SURSHUW\ FRQVLGHUDWLRQV EHFDXVH VROXELOLW\ DQG SURFHVVLQJ GLIILFXOWLHV PXVW DOZD\V EH GHDOW ZLWK LQ WKHVH V\VWHPV )LJXUH 6WUXFWXUHV RI SRO\SSKHQ\OHQHWHUHSKWKDODPLGHf f SRO\EHQ]RELVWKLD]ROHf f DQG SRO\SSKHQ\OHQHf f %DQGJDS )URP 'LHQHV WR ([WHQGHG &RQMXJDWLRQ 6\VWHPV 7KH VLPSOHVW RI WKH FRQMXJDWHG SRO\PHUV LV SRO\DFHW\OHQH &+ &+f ZKLFK ZDV V\QWKHVL]HG E\ =LHJOHU1DWWD SRO\PHUL]DWLRQ RI WKH PRQRPHULF JDV 7KH PDWHULDO LV RI

PAGE 16

‘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cMf IRU RUELWDOV SHUSHQGLFXODU WR RQH DQRWKHU DUH FRQVLGHUHG WR EH ]HUR 7KLV PHWKRG FDQ EH XWLOL]HG WR GHVFULEH WKH DURPDWLFLW\ LQ EHQ]HQH DQG FDQ EH H[WHQGHG WR OLQHDU FRQMXJDWHG V\VWHPV E\ WUHDWLQJ WKHP DV JLDQW F\FOLF VWUXFWXUHV ZLWK HTXDOO\ VSDFHG FDUERQV 2UELWDO HQHUJLHV DUH JLYHQ E\ WKH H[SUHVVLRQ ( D FRV"f§-f 9 f 79 ZKHUH LV WKH RUELWDO QXPEHU FRXQWLQJ XSZDUG IURP WKH ORZHVWHQHUJ\ RUELWDO DQG 1 LV WKH QXPEHU RI FDUERQ DWRPV DOVR WKH QXPEHU RI EDVLV RUELWDOVf LQ WKH FKDLQ 7KH ELQGLQJ HQHUJ\ RI DQ HOHFWURQ WR WKH S RUELWDO LV UHODWHG WR WKH &RXORPE LQWHJUDO D 7KH UHVRQDQFH LQWHJUDO LV UHODWHG WR WKH HQHUJ\ RI DQ HOHFWURQ LQ WKH ILHOG RI WZR QXFOHL 7KH PD[LPXP HQHUJ\ EHWZHHQ WKH ORZHVW DQG KLJKHVW PROHFXODU RUELWDOV LV DUELWUDULO\ VHW DW D FRQVWDQW YDOXH RI )LJXUH VKRZV WKH DSSOLFDWLRQ RI WKH )URVWfV FLUFOH PQHPRQLF WR LOOXVWUDWH WR HQHUJ\ OHYHOV IRU F\FOREXWDGLHQH DQG EHQ]HQH $V WKH QXPEHU RI OLQHDUO\ FRPELQHG DWRPLF RUELWDOV LQFUHDVH FRUUHVSRQGLQJ WR ODUJHU ULQJ VL]H LQ WKH )URVW FLUFOHf LW EHFRPHV FOHDU WKDW WKH HQHUJ\ GLIIHUHQFH EHWZHHQ PROHFXODU RUELWDOV EHFRPHV LQFUHDVLQJO\ VPDOO 7KH HQHUJ\ WR H[FLWH DQ HOHFWURQ IURP WKH +202 WR /802 OHYHO ZRXOG EH LQVLJQLILFDQW UHODWLYH WR WKH WKHUPDO HQHUJ\ RI DQ

PAGE 17

HOHFWURQ 7KH RUELWDOV ZRXOG PHUJH LQWR D RQHGLPHQVLRQDO EDQG VLPLODU WR WKH FRQGXFWLRQ EDQGV RI PHWDOV (OHFWURQV LQ WKH KLJKHVW HQHUJ\ RFFXSLHG RUELWDOV ZRXOG EH IUHH WR PRYH LQWR WKH XQRFFXSLHG RUELWDOV ZKHUH WKH\ ZRXOG KDYH D KLJK PRELOLW\ 7KLV VLPSOH PRGHO ZRXOG DOORZ IRU SRO\DFHW\OHQH WR EH PHWDOOLF ZLWK QR EDUULHU WR WKH IUHH PRYHPHQW RI HOHFWURQV LQ WKH V\VWHP PROHFXOH )URVWnV FLUFOH UHODWLYH RUELWDO PROHFXODU RUELWDOV HQHUJLHV RUELWDO W\SH DS DQWLERQGLQJ D QRQERQGLQJ D 3 ERQGLQJ D D DQWLERQGLQJ D S D 3 ERQGLQJ )LJXUH $SSOLFDWLRQ RI )URVWfV FLUFOH WR LOOXVWUDWH WKH HQHUJLHV RI PROHFXODU RUELWDOV ZLWKLQ F\FOLF V\VWHPV ([SHULPHQWV KDYH SURYHQ WKDW SRO\DFHW\OHQH LV QRW D PHWDOOLF FRQGXFWRU LQ LWV QHXWUDO VWDWH 7KLV LV DFFRXQWHG IRU E\ DQDO\]LQJ WKH RUELWDOV DW WKH )HUPL OHYHO 7KH )HUPL OHYHO LV WKH HQHUJ\ OHYHO ZKLFK KDV D b FKDQFH RI EHLQJ RFFXSLHG E\ DQ HOHFWURQ DQG UHSUHVHQWV WKH PLGSRLQW LQ HQHUJ\ RI D V\PPHWULF KDOIILOOHG EDQG 7KH PROHFXODU RUELWDOV DW WKH )HUPL OHYHO DUH FORVH HQRXJK LQ HQHUJ\ WR EHKDYH DV LI GHJHQHUDWH 7KH -DKQ7HOOHU WKHRUHP SUHGLFWV WKDW ZKHQ GHJHQHUDWH RUELWDOV DUH XQHYHQO\ ILOOHG ZLWK

PAGE 18

HOHFWURQV WKH HQHUJ\ RI WKHVH RUELWDOV FKDQJH DV D FRQVHTXHQFH RI D V\PPHWU\ ORZHULQJ YLEUDWLRQ 7KH RUELWDOV EHFRPH QRQGHJHQHUDWH DQG WKH WRWDO HQHUJ\ RI WKH V\VWHP LV ORZHUHG ,Q VROLG VWDWH SK\VLFV WHUPLQRORJ\ WKH -DKQ7HOOHU HIIHFW LV NQRZQ DV D 3HLHUOV GLVWRUWLRQ DQG RSHQV D JDS LQ WKH S] EDQG ZKLFK SK\VLFDOO\ GLVWRUWV WKH SRO\PHU FKDLQ WR DFKLHYH D ORZHU HQHUJ\ )LJXUH JUDSKLFDOO\ UHSUHVHQWV WKH HIIHFW RI WKH 3HLHUOV GLVWRUWLRQ RQ WKH EDQG VWUXFWXUH DQG GHQVLW\ RI VWDWHV '26f RI SRO\DFHW\OHQH )LJXUH DE ZRXOG H[HPSOLI\ D PHWDOOLF FRQGXFWRU ZLWK QR HQHUJ\ GLIIHUHQFH IRU HOHFWURQV WR PLJUDWH LQWR WKH XQILOOHG FRQGXFWLRQ EDQG )LJXUH OFG GHPRQVWUDWHV WKDW DV DGMDFHQW FDUERQV DORQJ WKH SRO\PHU FKDLQ GLPHUL]H DOWHUQDWH VLQJOH DQG GRXEOH ERQGV DUH IRUPHG DV D GLVFUHWH HQHUJ\EDQG JDS GHYHORSV (Jf 7KH S] EDQG LV EURNHQ LQWR DQ HPSW\ FRQGXFWLRQ DQG D IXOO YDOHQFH EDQG 3RO\DFHW\OHQH LV D VHPLFRQGXFWRU D n 6 FPnf ZLWK D EDQGJDS (Jf RI H9 3RO\DFHW\OHQH FDQ UHDFK FRQGXFWLYLWLHV RQ WKH RUGHU RI 6 FPn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

PAGE 19

DFWLYH UHVHDUFK DUHDV RI SRO\PHU FKHPLVWU\ 7KH LPSRUWDQFH RI WKH HDUO\ ZRUN RQ SRO\DFHW\OHQH ZDV FRQILUPHG E\ WKH DZDUGLQJ RI WKH 1REHO 3UL]H LQ &KHPLVWU\ WR )LJXUH %DQG VWUXFWXUH DQG GHQVLW\ RI VWDWHV '26f GLDJUDP RI D VLPSOH RQH GLPHQVLRQDO PHWDO SRO\DFHW\OHQHf SULRU WR DQG DIWHU D 3HLHUOV GLVWRUWLRQ Df %DQG VWUXFWXUH SULRU Ef '26 SULRU Ff %DQG VWUXFWXUH DIWHU 3HLHUOV GLVWRUWLRQ Gf '26 DIWHU 3HLHUOV GLVWRUWLRQ (J LV WKH EDQGJDS ZKLFK IRU D VHPLFRQGXFWRU VXFK DV SRO\DFHW\OHQH LV WZLFH WKH DFWLYDWLRQ HQHUJ\ IRU FRQGXFWLRQ

PAGE 20

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f FDWDO\]HG FRXSOLQJ UHDFWLRQV WR WKH SUHSDUDWLRQ RI FRQMXJDWHG SRO\PHUV /XPLQHVFHQFH 3KRWR DQG (OHFWUR 0XFK RI WKH GLVFXVVLRQ DQG JUDSKLFDO UHSUHVHQWDWLRQV SUHVHQWHG LQ WKLV LQWURGXFWLRQ WR WKH HOHFWUROXPLQHVFHQFH RI FRQMXJDWHG SRO\PHUV LV EDVHG RQ WKH UHYLHZ RI WKH WRSLF E\ 5LFKDUG + )ULHQG DQG 1HLO & *UHHQKDP LQ f(OHFWUROXPLQHVFHQFH LQ &RQMXJDWHG 3RO\PHUf LQ 7KH +DQGERRN RI &RQGXFWLQJ 3RO\PHUV VHH 5HI f 3OHDVH UHIHU WR WKLV UHIHUHQFH IRU D PRUH FRPSOHWH GLVFXVVLRQ RI WKH WHFKQLFDO VSHFLILFV IRU FRQVWUXFWLRQ DQG SURSHUWLHV RI OLJKW HPLWWLQJ GLRGHV /('fVf (OHFWUROXPLQHVFHQFH LV WKH JHQHUDWLRQ RI OLJKW E\ HOHFWULFDO H[FLWDWLRQ DQG ZDV ILUVW UHSRUWHG IRU DQ RUJDQLF VHPLFRQGXFWRU LQ E\ WKH REVHUYHG HPLVVLRQ RI OLJKW IURP VLQJOH FU\VWDOV RI DQWKUDFHQH 6WXGLHV RQ WKHVH VLPSOH HOHFWUROXPLQHVFHQW RUJDQLF VHPLFRQGXFWRUV HVWDEOLVKHG WKDW WKH SURFHVV UHVSRQVLEOH IRU WKH HPLVVLRQ RI OLJKW UHTXLUHV WKH LQMHFWLRQ RI HOHFWURQV IURP RQH HOHFWURGH DQG KROHV IURP WKH RWKHU WKH FDSWXUH RI RQH

PAGE 21

E\ WKH RWKHU UHFRPELQDWLRQf DQG WKH UDGLDWLYH GHFD\ RI WKH H[FLWHG VWDWH H[FLWRQf 7KH ILUVW H[DPSOH RI HOHFWUROXPLQHVFHQFH IURP D FRQMXJDWHG SRO\PHU ZDV ILUVW UHSRUWHG LQ XVLQJ SRO\SSKHQ\OHQHYLQ\OHQHf>339@ DV WKH VHPLFRQGXFWRU EHWZHHQ PHWDOOLF HOHFWURGHV ,Q /('f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fV Q Qr EDQGJDS DQG UDGLDWLYHO\ GHFD\V WR HPLW OLJKW (PLVVLRQ VSHFWUD IRU WKH VDPH SRO\PHU H[FLWHG HLWKHU HOHFWULFDOO\ RU SKRWRO\WLFDOO\ DUH XVXDOO\ YHU\ VLPLODU LQGLFDWLQJ WKDW WKH H[FLWHG VWDWH UHVSRQVLEOH IRU OLJKW JHQHUDWLRQ LV LGHQWLFDO IRU ERWK PHWKRGV RI H[FLWDWLRQ f3RODURQLFf H[FLWHG VWDWHV DUH IRUPHG DORQJ WKH SRO\PHU GXH WR WKH DELOLW\ RI SRO\PHUV WR UHDUUDQJH FKDLQ JHRPHWU\ WR UHGXFH WKH VWUDLQ WKDW FDQ EH SURGXFHG E\ WKH FKDUJHG H[FLWDWLRQV H[FLWRQVf 3RO\DFHW\OHQH KDV D GHJHQHUDWH JURXQG VWDWH DOORZLQJ IRUPDWLRQ RI VROLWRQOLNH FKDLQ H[FLWDWLRQV ZLWK D QRQERQGLQJ Q OHYHO LQ WKH PLGGOH RI WKH Q WLr VHPLFRQGXFWRU JDS ,Q SRO\PHUV ZLWK QRQGHJHQHUDWH JURXQG VWDWHV WKH WZR VHQVHV RI ERQG DOWHUQDWLRQ GR QRW KDYH HTXLYDOHQW HQHUJLHV 7KH FKDUJHG H[FLWDWLRQV RI D QRQGHJHQHUDWH JURXQGVWDWH SRO\PHU DUH WHUPHG SRODURQV RU ELSRODURQV DQG UHSUHVHQW ORFDOL]HG FKDUJHV RQ WKH SRO\PHU FKDLQ )LJXUH VKRZV WKH QRQGHJHQHUDF\ RI 339 DORQJ ZLWK D VFKHPDWLF UHSUHVHQWDWLRQ RI DQ LQWUDFKDLQ H[FLWRQ 7ZR QRQERQGLQJ PLGJDS

PAGE 22

fVROLWRQf VWDWHV IRUP ERQGLQJ DQG DQWLERQGLQJ FRPELQDWLRQV SURGXFLQJ WZR JDS VWDWHV V\PPHWULFDOO\ GLVSODFHG DERXW WKH PLGJDS VHH )LJXUH f 7KH OHYHOV FDQ EH RFFXSLHG E\ WR HOHFWURQV JLYLQJ D SRVLWLYH ELSRODURQ ESf SRVLWLYH SRODURQ Sf SRODURQ H[FLWRQ QHJDWLYH SRODURQ Snf RU QHJDWLYH ELSRODURQ ES f JURXQG VWDWH H[FLWHG VWDWH H[FLWRQ )LJXUH *HRPHWULFDO UHOD[DWLRQ RI D 339 FKDLQ LQ UHVSRQVH WR SKRWR RU HOHFWR H[FLWDWLRQ UF FRQGXFWLRQ EDQG OXPLQHVFHQFH W ES S SRODURQ 3 ESf Q YDOHQFH EDQG H[FLWRQ )LJXUH 3RODURQ ELSRODURQ DQG VLQJOHW H[FLWRQ HQHUJ\ OHYHOV LQ D QRQGHJHQHUDWH JURXQGVWDWH SRO\PHU 6LQJOHW DQG WULSOHW H[FLWRQV KDYH EHHQ VKRZQ WR H[LVW LQ FRQMXJDWHG SRO\PHUV 7DNLQJ LQWR DFFRXQW ERWK &RXORQELF DQG HOHFWURQODWWLFH LQWHUDFWLRQV WKH WULSOHW H[FLWRQ DQG VLQJOHW H[FLWRQ DUH QR ORQJHU RI WKH VDPH HQHUJ\ QRU RI WKH VDPH VL]H 7KH WULSOHW H[FLWRQ EHFRPHV PRUH ORFDOL]HG WKDQ WKH VLQJOHW H[FLWRQ ZKLFK PD\ H[WHQG RYHU VHYHUDO

PAGE 23

SRO\PHU UHSHDW XQLWV &DOFXODWLRQV KDYH VKRZQ WKDW WKH WULSOHW H[FLWRQ LV VWDELOL]HG E\ H9 ZLWK UHVSHFW WR WKH VLQJOHW H[FLWRQ DQG LV ORFDOL]HG RYHU QRW PXFK PRUH WKDQ D VLQJOH SRO\PHU UHSHDW XQLW IRU 339 )LJXUH VKRZV WKH UHODWLYH DUUDQJHPHQW RI JURXQG DQG H[FLWHG VWDWH HQHUJLHV IRU D FRQMXJDWHG SRO\PHU LQFOXGLQJ WKH H[SHULPHQWDOO\ PHDVXUHG KLJKHU HQHUJ\ WULSOHW 7rf 7\SLFDOO\ H[FLWDWLRQ RFFXUV WR D VLQJOHW H[FLWRQ WKDW XQGHUJRHV VRPH YLEUDWLRQDO UHOHDVH RI HQHUJ\ DQG WKHQ UHWXUQV WR WKH JURXQG VWDWH YLD WKH UHOHDVH RI OLJKW HQHUJ\ 7KH UHOD[DWLRQ EHIRUH HPLVVLRQ RI OLJKW UHVXOWV LQ WKH HQHUJ\ RI HPLWWHG OLJKW EHLQJ RI VOLJKWO\ ORZHU HQHUJ\ WKDQ WKH HQHUJ\ RI WKH Q WR Qr OHYHO 6WRNHfV VKLIWf VLQJOHW WULSOHW 7 LQWHUn V\VWHP FURVVLQJ DEVRUSWLRQ LQGXFHG DEVRUSWLRQ OXPLQHVFHQFH )LJXUH (OHFWURQLF WUDQVLWLRQV LQ D FRQMXJDWHG SRO\PHU LH 339f VKRZLQJ ERWK VLQJOHW DQG WULSOHW VWDWHV &RQMXJDWHG 3RO\PHUV IRU (OHFWURDFWLYH $SSOLFDWLRQV &RQWURO RI WKH Q WR Qr HQHUJ\ JDS RI D FRQMXJDWHG SRO\PHU LV RI XWPRVW LPSRUWDQFH LQ RUGHU WR WXQH WKH ZDYHOHQJWK RI HPLWWHG OLJKW WKURXJK WKH YLVLEOH OLJKW UHJLRQ 7KH HQHUJ\ JDS FDQ EH PRGLILHG E\ GLUHFWO\ FKDQJLQJ WKH W\SH RI FRQMXJDWLRQ

PAGE 24

7DEOH %ULHI 6XPPDU\ RI (PLVVLRQ :DYHOHQJWK IRU 'LIIHULQJ &RQMXJDWHG 3RO\PHU 6WUXFWXUHV DORQJ WKH EDFNERQH DGGLWLRQ RI VLGHFKDLQ JURXSV ZLWK HOHFWURQ GRQDWLQJ RU HOHFWURQ ZLWKGUDZLQJ VXEVWLWXHQWV RU GLVUXSWLRQ RI FRQMXJDWLRQ OHQJWK E\ LQVHUWLRQ RI QRQ FRQMXJDWHG VHJPHQWV 7KH PRUH HOHFWURQ ULFK D V\VWHP LV WKH IDUWKHU LQWR WKH ORZHU HQHUJ\ UHG HPLVVLRQ SRUWLRQ RI WKH YLVLEOH VSHFWUXP LW ZLOO EH (OHFWURQ GHILFLHQW SRO\PHUV ZLOO HPLW LQ WKH KLJKHU EOXH HPLVVLRQ SRUWLRQ RI WKH VSHFWUXP

PAGE 25

%OXH HPLVVLRQ LV IRXQG LQ SRO\"SKHQ\OHQHf 333f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fV 0DQ\ YDULDWLRQV DQG PHWKRGV RI GHYLFH FRQVWUXFWLRQ KDYH EHHQ DWWHPSWHG RYHU WKH ODVW GHFDGH ZLWK WKH DERYH SRO\PHU W\SHV DQG RWKHUV WR LPSURYH GHYLFH RXWSXW 'LVFXVVLRQ RI DOO WKH YDULDWLRQV LQ /(' FRQVWUXFWLRQ ZLOO QRW EH SUHVHQWHG KHUH GXH WR WKH IRFXV RI WKLV UHVHDUFK EHLQJ DLPHG DW WKH V\QWKHVHV RI QHZ FRQMXJDWHG SRO\PHUV ,Q SDUWLFXODU D IRFXVHG GLVFXVVLRQ RI WKH SDOODGLXP2f FDWDO\]HG 6X]XNL 6WLOOH DQG 6RQDJDVKLUD FRXSOLQJ UHDFWLRQV ZLOO EH FRQGXFWHG 3DOODGLXP2f &RXSOLQJ 5HDFWLRQV $Q LPSRUWDQW FRPSRQHQW ZDV DGGHG WR WKH WRROER[ RI WKH V\QWKHWLF RUJDQLF FKHPLVW LQ WKH HDUO\ fV E\ WKH GHYHORSPHQW RI FURVV FRXSOLQJ UHDFWLRQV LQYROYLQJ PHWDO FDWDO\VLV RI RUJDQRPHWDOOLF VSHFLHV (TXDWLRQ LOOXVWUDWHV WKH VLPSOH SULQFLSOHV LQYROYHG LQ D FURVV FRXSOLQJ UHDFWLRQ 5 DQG 5f DUH W\SLFDOO\ VS K\EULGL]HG FDUERQ

PAGE 26

5 0 5ff§; 5f§5f>ZLWK 3Gf FDWDO\VW@ f VSHFLHV 0 LV D PHWDO WLQ ERURQ HWFf DQG ; LV D KDORJHQ RU WULIODWH 3DOODGLXP FDWDO\]HG UHDFWLRQV RI *ULJQDUG UHDJHQWV ZDV ILUVW UHSRUWHG E\ @ f WUDQVPHWDOODWLRQ ZKHUHLQ D VHFRQG DU\O JURXS LV WUDQVIHUUHG IURP WKH PHWDOODWHG VSHFLHV WR 3G DQG f UHGXFWLYH HOLPLQDWLRQ RI D ELDU\O VSHFLHV VHH )LJXUH f ,I GLIXQFWLRQDO PHWDOODWHG DQG DU\O KDOLGH UHDJHQWV DUH XVHG ROLJRPHULF DQG SRO\PHULF PDWHULDOV PD\ UHVXOW (OHFWURQ ZLWKGUDZLQJ JURXSV IDFLOLWDWH WKH R[LGDWLYH DGGLWLRQ VWHS ZKLOH WKH QDWXUH RI WKH KDOLGH RU OHDYLQJ JURXS DIIHFWV WKH UHDFWLRQ UDWH IROORZLQJ WKH WUHQG ,!27I!%U}&O 7KH WUDQVPHWDOODWLRQ VWHS PD\ EH UDWH OLPLWLQJ LI WKH PHWDOODWHG VSHFLHV LV VWHULFDOO\ KLQGHUHG

PAGE 27

; %U HWF 0 %25f 6Q5 HWF )LJXUH *HQHUDO FDWDO\WLF F\FOH IRU 3Gf FURVV FRXSOLQJ UHDFWLRQV 5HDFWLRQV DUH FRQGXFWHG XQGHU DQDHURELF FRQGLWLRQV LQ D YDULHW\ RI VROYHQWV VXFK DV 7+) '0) DQG WROXHQH )RU WKH 6X]XNL UHDFWLRQ ZDWHU DQG EDVH DUH DGGHG WR DFFHOHUDWH WKH IRUPDWLRQ RI D PRUH DFWLYH ERURQDWH DQLRQ IRU WKH WUDQVPHWDOODWLRQ VWHS RWKHUZLVH WKH RWKHU PHWKRGV DUH SHUIRUPHG LQ GU\ VROYHQW 3G,,f FDWDO\VWV VXFK DV 3G&O33Kf DUH XVXDOO\ HPSOR\HG LQ WKH UHDFWLRQV GXH WR WKHLU JHQHUDO VWRUDJH DQG KDQGOLQJ DGYDQWDJHV RYHU 3Gf FDWDO\VWV VXFK DV 3G33Kf ZKLFK DUH DLU DQG PRLVWXUH VHQVLWLYH :KHQ XVLQJ D 3G,,f FRPSRXQG WKH UHGXFWLRQ RI WKH 3G,,f VSHFLHV WR 3Gf PXVW RFFXU EHIRUH WKH F\FOH FDQ EHJLQ 7KH H[DFW QDWXUH RI WKLV FRQYHUVLRQ LV GHEDWHG EXW PD\ LQFOXGH WKH KRPRFRXSOLQJ RI WKH PHWDOODWHG VSHFLHV /LJDQGV SUHVHQW RQ WKH 3G DLG

PAGE 28

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fKDUPOHVVf 7KH GUDZEDFN WR WKH 6X]XNL UHDFWLRQ LV WKDW IRU PDQ\ HOHFWURQ ULFK DU\O JURXSV ERURQLF HVWHUV RU DFLGV DUH PXFK WRR XQVWDEOH WR ZLWKVWDQG WKH QXPHURXV FRXSOLQJV QHHGHG IRU SRO\PHUL]DWLRQ 2EYLRXVO\ WKH +HFN DQG 6RQRJDVKLUD UHDFWLRQV DUH DSSOLHG VSHFLILFDOO\ WR WKH IRUPDWLRQ RI YLQ\OHQH DQG HWK\Q\OHQH OLQNDJHV DQG DUH QRW DOWHUQDWLYHV WR PDQ\ 6X]XNL RU 6WLOOH URXWHV 7KH UHDJHQWV IRU HDFK DUH IDLUO\ VWDEOH RUJDQLFV DQG WKH E\n SURGXFWV RI WKH FDWDO\WLF F\FOH DUH PLQHUDO DFLGV 7KH SDOODGLXP f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f RI WRWDO KDORJHQ WR PHWDO IXQFWLRQDOLW\ PXVW EH PDLQWDLQHG DV

PAGE 29

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r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

PAGE 30

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n &RQMXJDWHG VWLIIFKDLQ SRO\HOHFWURO\HV UHPDLQ LQ DQ H[WHQGHG FRQIRUPDWLRQ UHJDUGOHVV RI WKH LRQLF VWUHQJWK RI WKH VROXWLRQ (IIHFWV REVHUYHG IURP ORZHULQJ WKH LRQLF VWUHQJWK RI WKH V\VWHP PXVW WKHUHIRUH EH GXH WR LQWHUPROHFXODU IRUFHV &RQMXJDWHG SRO\HOHFWURO\WHV UHSUHVHQW LQWHUHVWLQJ PRGHOV IRU VWXG\LQJ WKH VFUHHQHG FRXORPELF LQWHUDFWLRQV LQ SRO\PHULF V\VWHPV ,QWHUHVWLQJ DSSOLFDWLRQV PD\ DOVR EH DYDLODEOH IRU WKHVH PDWHULDOV LQ PHPEUDQH PDQXIDFWXULQJ 6SHFLILFV DQG UHIHUHQFHV IRU OLWHUDWXUH H[DPSOHV RI FRQMXJDWHG SRO\HOHFWURO\WHV V\QWKHVL]HG E\ SDOODGLXP f FDWDO\VLV ZLOO EH JLYHQ LQ WKH LQWURGXFWLRQ WR &KDSWHU 6FRSH RI WKH 'LVVHUWDWLRQ 7KLV ERG\ RI ZRUN IRFXVHV RQ LQFRUSRUDWLRQ RI TXDWHPL]HG GLDONR[\DPLQH SKHQ\OHQH RU TXDWHPL]HG GLDON\ODPLQHSKHQ\OHQH VDOW PRLHWLHV LQWR WKH EDFNERQH RI FRQMXJDWHG SRO\PHUV 6X]XNL 6WLOOH 6RQDJDVKLUD +HFNf DQG $',0(7 SRO\PHUL]DWLRQ WHFKQLTXHV ZLOO EH XVHG WR V\QWKHVL]H QHXWUDO SRO\PHUV RI WKH IROORZLQJ W\SHV SRO\" SKHQ\OHQHf>333@ SRO\"SKHQ\OHQHFRWKLRSKHQHf>337@ DQG SRO\"SKHQ\OHQHFR HWK\Q\OHQHf>33(@ ZKHUHE\ WKH SKHQ\OHQH SRUWLRQ RI WKH UHSHDW XQLW LV LQLWLDOO\

PAGE 31

V\QWKHVL]HG ZLWK QHXWUDO DONR[\WULHWK\ODPLQH RU DON\OEURPLGH VLGH FKDLQV 7KHVH QHXWUDO SRO\PHUV FDQ EH DQDO\]HG XVLQJ WUDGLWLRQDO WHFKQLTXHV *3& 105 HWFf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

PAGE 32

&+$37(5 &$7,21,& 32/<"3+(1
PAGE 33

WKDW GR QRW UHIOHFW WKH FKDUDFWHULVWLFV RI SXUH 333 7KHUPDO PHFKDQLFDO DQG FKHPLFDO VWDELOLW\ DUH UHGXFHG DQG WKH RSWLFDO DEVRUSWLRQ DQG HPLVVLRQ ZDYHOHQJWKV DUH VKLIWHG IURP WKH H[SHFWHG YDOXHV 1HYHUWKHOHVV WKH PROHFXODU ZHLJKW HQKDQFHPHQWV DQG VROXELOLW\ RI UHVXOWLQJ VXEVWLWXWHG 333fV RIWHQ RXWZHLJK WKH SURSHUW\ GLIIHUHQFHV EHWZHHQ WKHPVHOYHV DQG fSXUH 333f $ VHFRQG KLQGUDQFH WR 333 V\QWKHVLV LV WKDW WUDGLWLRQDO SRO\PHUL]DWLRQ WHFKQLTXHV DUH QRW GHVLJQHG WR JURZ D FKDLQ YLD FDUERQFDUERQ ERQG IRUPDWLRQ EXW W\SLFDOO\ YLD FDUERQKHWHURDWRP R[\JHQ RU QLWURJHQf FRXSOLQJ 2IWHQ WKH VRPHZKDW fH[RWLFf PHWKRGV XVHG WR FUHDWH 333 DFWXDOO\ HQKDQFH VLGH UHDFWLRQV OHDGLQJ WR VWUXFWXUDOO\ SRRU SRO\PHUV (OHFWURFKHPLFDO SRO\PHUL]DWLRQV KDYH EHHQ DWWHPSWHG ERWK R[LGDWLYHO\ ZLWK GLDONR[\EHQ]HQHV DQG UHGXFWLYHO\ ZLWK GLKDOREHQ]HQHV LQ WKH SUHVHQFH RI D QLFNHO FDWDO\VW &KHPLFDO R[LGDWLRQ SRO\PHUL]DWLRQV KDYH EHHQ FRQGXFWHG ZLWK FXSULF FKORULGH )LJXUH ODf 7KHUPDO FRQYHUVLRQ RI UDGLFDOO\ RU WUDQVLWLRQ PHWDO SRO\PHUL]HG SURWHFWHG GLK\GUR[\F\FORKH[DGLHQH WR XQVXEVWLWXWHG 333 RYHUFDPH VROXELOLW\ GLIILFXOWLHV ZLWK VROXEOH fSUHSRO\PHUf LQWHUPHGLDWHV WKDW FDQ EH SURFHVVHG DQG VXEVHTXHQWO\ FRQYHUWHG WR fSXUH 333f )LJXUH OEf 7KHUPDO F\FOL]DWLRQ RI HQHGL\QHV DQG RSKHQ\OGL\QHV JDYH 333fV DQG SRO\OQDSKWK\OHQHVf UHVSHFWLYHO\ )LJXUH OFf 1LFNHO FDWDO\]HG *ULJQDUG FRXSOLQJV RI GLEURPREHQ]HQH KDYH DOVR EHHQ SHUIRUPHG E\
PAGE 34

GLPHWKDQHVXOIRQ\Of DQG GLWULIOXRURPHWKDQHVXOIRQ\Of EHQ]HQHV LQ WKH SUHVHQFH RI H[FHVV ]LQF KDYH DIIRUGHG IXQFWLRQDOL]HG 333fV )LJXUH OHI f )LJXUH 6\QWKHWLF PHWKRGV WR SRO\SSKHQ\OHQHf Hf If 6X]XNL &RXSOLQJV $ PDMRU LPSURYHPHQW LQ 333 V\QWKHVLV FDPH LQ ZKHQ 5HKDKQ DQG FRZRUNHUV DSSOLHG WKH PRUH UHDFWLYH 6X]XNL FRXSOLQJ UHDFWLRQ PHWKRGRORJ\ WR WKH

PAGE 35

SRO\PHUL]DWLRQ $% SRO\PHUL]DWLRQ RI EURPRGLDON\OEHQ]HQHERURQLF DFLGV DQG $$%% SRO\PHUL]DWLRQ RI OGLEURPRGLDON\OEHQ]HQHERURQLF DFLGV ZDV SHUIRUPHG )LJXUH f &KDLQ OHQJWKV RI ULQJV ZHUH DFKLHYHG OHDGLQJ WR SURFHVVDEOH VXEVWLWXWHG 333fV 7KH VXFFHVV RI WKH 6X]XNL UHDFWLRQ ZLWK LWV XVH RI OHVV HOHFWURSRVLWLYH ERURQ UHDJHQWV KLJK \LHOG FRXSOLQJV DQG WROHUDQFH IRU PL[HG DTXHRXV RUJDQLF VROYHQW V\VWHPV RSHQHG WKH GRRU WR D YDULHW\ RI IXQFWLRQDOL]HG 333fV KLWKHUWR XQUHDFKDEOH 2QH RI WKH PRVW LQWHUHVWLQJ VXEILHOGV WR DULVH IURP WKLV PHWKRGRORJ\ ZDV WKH V\QWKHVLV RI FRQMXJDWHG ULJLG SRO\HOHFWURO\WHV 7KH ILUVW URGOLNH SRO\HOHFWURO\WHV ZHUH UHSRUWHG LQ WKH HDUO\ fV DQG ZHUH EDVHG XSRQ SRO\OSKHQ\OHQHEHQ]RELVR[D]ROHf DQG SRO\O &7 SKHQ\OHQHEHQ]RELVWKLD]ROHf &DUHIXO LQFRUSRUDWLRQ RI DQLRQLF RU FDWLRQLF IXQFWLRQDOLW\ LQWR D 333 \LHOGV D PDWHULDO WKDW SRVVHVVHV WKH EHQHILFLDO SURSHUWLHV RI D FRQMXJDWHG SRO\PHU ZLWK WKH DTXHRXV VROXELOLW\ DQG SURFHVVDELOLW\ RI D SRO\HOHFWURO\WH 7KH HQYLURQPHQWDO XWLOLW\ RI DTXHRXV SURFHVVLQJ WHFKQLTXHV DSSOLFDEOH WR SRO\HOHFWURO\WHV LV D SRWHQWLDO DGYDQWDJH RI WKHVH PDWHULDOV IRU XVH LQ DQ LQGXVWULDO VHWWLQJ &DUER[\ODWH )LJXUH DEf VXOIRQDWH )LJXUH Ff DQG VXOIRQDWRSURSR[\ JURXSV )LJXUH Gf KDYH EHHQ XVHG WR FUHDWH DQLRQLF 333 SRO\HOHFWURO\WHV )LJXUH 6X]XNL FRXSOLQJ DSSURDFKHV WR VXEVWLWXWHG SRO\!SKHQ\OHQHf

PAGE 36

&22+ &22+ 3 R ? &+f U n2D6 )LJXUH $QLRQLF SRO\SSKHQ\OHQHfnV UHSRUWHG LQ WKH OLWHUDWXUH +LJKO\ FKDUJHG FDWLRQLF DPPRQLXP DQG S\ULGLQLXP 333 SRO\HOHFWURO\WHV ZHUH UHSRUWHG LQ WKH PLG fV E\ 5HKDKQ DQG FRZRUNHUV )LJXUH DEf 'U 3HWHU % %DODQGD RI WKH 5H\QROGVf UHVHDUFK JURXS XVHG DQ DOWHUQDWH PHWKRGRORJ\ WR LQFOXGH FR FDWLRQLF TXDWHUQDU\ DPPRQLXP VDOW VLGH FKDLQV LQWR D 333 EDFNERQH )LJXUH Ff 3RO\ >ELV ^1 1 $WULHWK\ODPPRQLXP` R[DSURS\OfSKHQ\OHQHDW SKHQ\OHQH@ GLEURPLGH 3331(/f ZDV V\QWKHVL]HG YLD D 6X]XNL SURWRFRO 7KH SRO\PHU ZDV XVHG LQ WKH DVVHPEO\ RI EOXH HPLWWLQJ VROLG VWDWH GHYLFHV YLD OD\HUE\OD\HU SRO\HOHFWURO\WH VHOIDVVHPEO\ ZLWK VXOIRQDWRSURSR[\ 333 7KH PDWHULDO DOVR SURYHG YHU\ XVHIXO DV D EXIIHU OD\HU IRU K\EULG LQNMHW SULQWHG /('fV XVLQJ VXOIRQDWRSURSR[\ VXEVWLWXWHG SRO\SKHQ\OHQHYLQ\OHQHVf

PAGE 37

)LJXUH &DWLRQLF SRO\"SKHQ\OHQHfnV UHSRUWHG LQ WKH OLWHUDWXUH 5 KH[\Of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fSXUH 333f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

PAGE 38

f ZDV LRGRQDWHG XQGHU DFLGLF FRQGLWLRQV XVLQJ SRWDVVLXP SHULRGDWH LRGLQH DQG D PL[HG VROYHQW V\VWHP FRQVLVWLQJ RI +2 $F + +6E\ YROXPH ZLWK KHDWLQJ WR \LHOG GLPHWKR[\OGLLRGREHQ]HQH f &RPSRXQG ZDV UHDFWHG ZLWK ERURQ WULEURPLGH LQ PHWK\OHQH FKORULGH DW r& SURGXFLQJ GLLRGRK\GURTXLQRQH ',+4f ,W VKRXOG EH QRWHG WKDW ERURQ WULEURPLGH LV D YHU\ UHDFWLYH UHDJHQW ZLWK ODUJH DPRXQWV RI +%U JDV OLEHUDWHG GXULQJ WKH DTXHRXV ZRUNXS RI WKH UHDFWLRQ ',+4 LV UHFRYHUHG DV D FUXGH EURZQ VROLG 5HFU\VWDOOL]DWLRQ IURP 7+) DQG KH[DQH DIIRUGV FRORUOHVV FU\VWDOV RI SXUH SURGXFW %RWK VWHSV DUH KLJK \LHOGLQJ b DQG bf ZLWK DQ RYHUDOO b \LHOG EDVHG RQ VWDUWLQJ PDWHULDO $QDO\VLV RI WKH FUXGH PDWHULDO E\ f+ 105 VKRZV WKH RQO\ RUJDQLF SURGXFW ZDV WKH GHVLUHG FRPSRXQG ,W ZDV ODWHU IRXQG WKDW XVH RI WKLV EURZQ PDWHULDO ZDV VXIILFLHQW IRU WKH :LOOLDPVRQ HWKHULILFDWLRQV WR IROORZ b \LHOG RI WKH FUXGH PDWHULDO ZDV REWDLQHG KFR 2&+ NLRL $F2+ + +6 r& K b )LJXUH &RQYHUVLRQ RI GLPHWKR[\EHQ]HQH WR GLLRGRK\GURTXLQRQH GLEURPRK\GURTXLQRQH '%+4f ZDV V\QWKHVL]HG LQ b \LHOG IURP WKH GLUHFW EURPLQDWLRQ RI K\GURTXLQRQH f LQ PHWK\OHQH FKORULGH DQG DFHWLF DFLG 7KH UHDFWLRQ SURFHHGV WKURXJK WKUHH VWDJHV 7KH LQLWLDO VHWXS LQYROYHV WKH VXVSHQVLRQ RI K\GURTXLQRQH LQ WKH VROYHQW V\VWHP $V WKH ILUVW HTXLYDOHQW RI EURPLQH LV DGGHG WKH UHVXOWLQJ PRQREURPLQDWHG VSHFLHV HQWHUV VROXWLRQ DQG DV WKH VHFRQG EURPLQH DGGV WR WKH SKHQ\O ULQJ WKH GHVLUHG SURGXFW SUHFLSLWDWHV RXW RI VROXWLRQ PDNLQJ SURGXFW UHFRYHU\ D VLPSOH

PAGE 39

PDWWHU RI ILOWUDWLRQ 7KH UHDFWLRQfV ORZHU \LHOG LV SUREDEO\ D UHVXOW RI VRPH '%+4 UHPDLQLQJ GLVVROYHG LQ WKH VROYHQW 1R DWWHPSWV ZHUH PDGH WR UHFRYHU WKLV fORVWf PDWHULDO 5HFU\VWDOOL]DWLRQ RI WKH VOLJKWO\ SLQN FUXGH SURGXFW IURP D KRW YYf ZDWHU WR LVRSURSDQRO VROYHQW VROXWLRQ UHPRYHG WKH XQGHVLUHG LPSXULWLHV 2+ HT %U 0H&,R $F2+ +2 '%+4 b )LJXUH %URPLQDWLRQ RI K\GURTXLQRQH LQ WKH SRVLWLRQV ',+4 DQG '%+4 ZHUH VXEMHFWHG WR :LOOLDPVRQ HWKHULILFDWLRQ FRQGLWLRQV LQ UHIOX[LQJ DFHWRQH ZLWK HTXLYDOHQWV RI FKORURWULHWK\ODPLQH K\GURFKORULGH f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b 7KH PRQRPHUV ZHUH LVRODWHG DQG UHFU\VWDOOL]HG WZLFH IURP PHWKDQRO ZDWHU WR DFKLHYH PD[LPXP SXULW\ DQG GULHG RYHU &D64r XQGHU YDFXXP WR HQVXUH GU\QHVV IRU WKH DFFXUDWH PDVV PHDVXUHPHQWV QHFHVVDU\ IRU VWHS JURZWK SRO\PHUL]DWLRQV '%1(W ZDV UHFRYHUHG LQ ORZHU \LHOG GXH WR ODUJHU DPRXQWV RI PDWHULDO EHLQJ ORVW GXULQJ WKH UHFU\VWDOOL]DWLRQ VWHSV

PAGE 40

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b ,VRODWLQJ WKH ERURQLF DFLG IROORZHG E\ WUDQVHVWHULILFDWLRQ XVLQJ EHQ]HQH WR D]HRWURSLFDOO\ GLVWLOO RII WKH +2 E\SURGXFW GLG QRW LPSURYH \LHOGV VXEVWDQWLDOO\ b JDLQf ; 3URGXFW b
PAGE 41

b )LJXUH 6\QWKHVLV RI GLERURQLF SKHQ\OHQH UHDJHQWV IRU XVH LQ 6X]XNL FRXSOLQJV )LJXUH RXWOLQHV WKH SUHSDUDWLRQ RI D WKUHH ULQJ PRGHO FRPSRXQG WKDW ZDV XVHG DV D JXLGH IRU DVVLJQLQJ SHDNV LQ WKH f+ DQG & 105 RI VXEVHTXHQW SRO\PHUV DQG DOVR DV D VWDQGDUG IRU OXPLQHVFHQFH VHQVLQJ VWXGLHV FRQGXFWHG ZLWK 'U .LUN 6FKDQ]H DQG %HQMDPLQ +DUULVRQ DW WKH 8QLYHUVLW\ RI )ORULGD 3KHQ\OERURQLF DFLG DQG 3G2$Ff ZHUH XVHG DV SXUFKDVHG IURP $OGULFK &KHPLFDO &RPSDQ\ &RQWDPLQDWLRQ RI WKH SURGXFW ZLWK 3Gf GRHV RFFXU ZKHQ XVLQJ 3G2$Ff DV LW ODFNV VROXELOL]LQJ OLJDQGV WR NHHS WKH FDWDO\VW IURP SUHFLSLWDWLQJ 7KLV ZLOO EH D PRUH GLIILFXOW LVVXH WR DGGUHVV LQ WKH SRO\PHU V\QWKHVHV WR IROORZ EXW WKH FRQWDPLQDWLRQ FRXOG HDVLO\ EH UHPRYHG IURP WKH ORZ PROHFXODU ZHLJKW FRPSRXQG E\ WKH DGGLWLRQ RI GHFRORUL]LQJ FDUERQ DQG ILOWUDWLRQ WKURXJK VHEDFHRXV HDUWK &HOLWHf 4XDWHPL]DWLRQ RI FRPSRXQG ZDV DFKLHYHG E\ VWLUULQJ LQ 7+) DQG EURPRHWKDQH DW r& IRU GD\V 'XULQJ WKH FRXUVH RI WKH UHDFWLRQ WKH GHVLUHG SURGXFW SUHFLSLWDWHG RXW RI VROXWLRQ 105 SHDN YDOXHV IRU ERWK FDQ EH IRXQG LQ &KDSWHU ([SHULPHQWDOf RI WKH GLVVHUWDWLRQ $V H[SHFWHG FRPSRXQGV DQG GLVSOD\ H[WUHPH VROXELOLW\ GLIIHUHQFHV &RPSRXQG LV VROXEOH LQ UHODWLYHO\ QRQn SRODU VROYHQWV VXFK DV KDORJHQDWHG RUJDQLFV &+&, DQG &+&,f DQG WKH PRUH SRODU 7+) ZKLOH FRPSRXQG LV VROXEOH LQ YHU\ SRODU VROYHQWV VXFK DV DFHWRQLWULOH DQG ZDWHU

PAGE 42

%RWK n+ 105 LQWHJUDWLRQ DQG HOHPHQWDO DQDO\VLV b %Uf LQGLFDWH D QHDUO\ TXDQWLWDWLYH OHYHO RI TXDWHPL]DWLRQ 1HXWUDO 3RO\PHU 6\QWKHVHV 7KH JHQHUDO 6X]XNL SRO\PHUL]DWLRQ LV RXWOLQHG LQ )LJXUH 7KH GLDONR[\DPLQHGLKDORJHQDWHG EHQ]HQH PRQRPHU ERURQLF UHDJHQW 3G FDWDO\VW RI FKRLFH DQG PLOG EDVH VXFK DV .&2 1D&&! RU 1D+&&! DUH VWLUUHG LQ D PL[HG DTXHRXV RUJDQLF 7+) '0) DFHWRQHf VROYHQW V\VWHP ZLWK KHDWLQJ WR r& 6SHFLDO FDUH LV WDNHQ WR HQVXUH WKDW WKH UHDFWLRQ YHVVHO DQG VROYHQWV DUH IXOO\ GHJDVVHG ZLWK $U SULRU WR DGGLWLRQ RI WKH FDWDO\VW DQG WKH UHDFWLRQ FRQGXFWHG XQGHU D EODQNHW RI WKH LQHUW JDV $WPRVSKHULF LQ WKH UHDFWLRQ PD\ FRQWULEXWH WR R[LGDWLRQ RI WKH 3G FDWDO\VW DQG GHFUHDVH LWV FDWDO\WLF DFWLYLW\ DQGRU LQFUHDVH WKH UDWH RI KRPRFRXSOLQJ RI WKH ERURQLF UHDJHQWV )LJXUH 6\QWKHVLV RI QHXWUDO DQG FDWLRQLF 333 PRGHO FRPSRXQGV

PAGE 43

7KH RULJLQDO SRO\PHUL]DWLRQV ZHUH FRQGXFWHG E\ 'U 3HWHU %DODQGD DQG IRFXVHG RQ WKH V\QWKHVLV RI 3331( 7KHVH LQLWLDO V\QWKHWLF LQYHVWLJDWLRQV XVHG '%1(W 3G2$Ff DV WKH FDWDO\VW ZLWK '0) 7+) DQG DFHWRQH DV VROYHQWV 8VDEOH SRO\PHULF PDWHULDOV ZHUH V\QWKHVL]HG ZLWK '0) SRO\PHUL]DWLRQV JLYLQJ WKH KLJKHVW PROHFXODU ZHLJKWV E\ *3& 6HYHUDO REVWDFOHV UHPDLQHG 8VLQJ 3G2$Ff DV FDWDO\VW UHVXOWHG LQ WKH SUHFLSLWDWLRQ RI EODFN PHWDOOLF 3G LQWR VROXWLRQ DQG FRQWDPLQDWLRQ RI WKH SRO\PHU 5HPRYDO RI WKLV LPSXULW\ RIWHQ SURYHG GLIILFXOW LI QRW LPSRVVLEOH DQG VRPH ORVV RI WKH SRO\PHU ZDV LQHYLWDEOH RU R R ; %U N& +S2 3G FDWDO\VW r& 0 : RUJDQLF VROYHQW 2 2 2 2 )LJXUH 6X]XNL SRO\PHUL]DWLRQV IRU QHXWUDO DONR[\DPLQH FRQWDLQLQJ 333fV

PAGE 44

.RZLW] DQG :HJQHU SXEOLVKHG UHVXOWV IURP 6X]XNL SRO\PHUL]DWLRQV XVLQJ WKH PRUH DFWLYH GLFKORUR>OUELVGLSKHQ\OSKRVSKLQRfIHUURFHQH@ SDOODGLXP ,,f >3G&EGSSIf@ DV FDWDO\VW LQ D 7+) EDVHG VROXWLRQ DW URRP WHPSHUDWXUH ZLWK YHU\ KLJK PROHFXODU ZHLJKWV DQG SHUFHQW FRQYHUVLRQ WR SRO\PHU 7KH PHWKRGRORJLHV SUHVHQWHG LQ UHIHUHQFH ZHUH DSSOLHG WR WKH V\QWKHVLV RI WKH DPLQH VXEVWLWXWHG 3331(W 7KH V\QWKHVLV RI 3G&EGSSIf ZDV ILUVW UHSRUWHG LQ E\ +D\DVKL HW DO 7KH 3G&ELGSSIf KDV WZR DGYDQWDJHV RYHU 3G2$Ff 7KH GSSI >GLSKHQ\OSKRVSKLQR IHUURFHQH@ OLJDQG SURYLGHV VROXELOLW\ WR WKH FDWDO\VW DV WKH SRO\PHUL]DWLRQ SURFHHGV WKXV SUHYHQWLQJ FRQWDPLQDWLRQ RI WKH SRO\PHU ZLWK EODFN 3Gf :LWK RQH REMHFWLYH WR LQFUHDVH VFDOH RI WKH UHDFWLRQ FRQWDPLQDWLRQ PXVW EH DYRLGHG WR SUHYHQW ORVV RI SURGXFW GXULQJ fFOHDQLQJf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fHWKDQH@ SDOODGLXP ,,f >3G&EGSSHf@ DQG GLFKORUR>OELVGLSKHQ\OSKRVSKLQRfSURSDQH@ SDOODGLXP ,,f >3G&ELGSSSf@ DORQJ ZLWK 3G&ELGSSIf DUH VKRZQ LQ )LJXUH 3G&OGSSIf KDV WKH VPDOOHVW &O3G&O ERQG DQJOH RI WKH WKUHH FDWDO\VWV rf ([SHULPHQWV E\ +L\DVKL DQG FRZRUNHUV UHYHDOHG D GLUHFW UHODWLRQVKLS EHWZHHQ WKH &O3G&O ERQG DQJOH DQG FDWDO\VW HIILFLHQF\f 7KH WZR FKORULQH OLJDQGV RFFXS\ WKH VLWHV ZKHUH WKH VSHFLHV WR EH FRXSOHG ZLOO HYHQWXDOO\ UHVLGH EHIRUH UHGXFWLYH HOLPLQDWLRQ 7KH UHGXFHG DQJOH OHDGV WR D UDWH

PAGE 45

LQFUHDVH LQ WKH UHGXFWLYH HOLPLQDWLRQ VWHS ZKLFK LV RIWHQ WKH UDWH OLPLWLQJ VWHS LQ 6X]XNL FRXSOLQJV WKXV LQFUHDVLQJ WKH RYHUDOO UDWH RI WKH UHDFWLRQ 3RO\PHUL]DWLRQV RI ELVQHRSHQW\OJO\FROOSKHQ\OHQHGLERURQDWH DQG '%1(W ZLWK 3G&OGSSIf LQ 7+) DT 1D+&&! DW r& IRU GD\V \LHOGHG LPSURYHPHQWV RYHU SUHYLRXV ZRUN >3331(WGSSIf>@@ $ SRO\PHU ZLWK KLJKHU PROHFXODU ZHLJKW 0Q JPRO >FRPSDUHG WR JPRO IRU 3G2$Ff LQ '0) SRO\PHU 333 1(W%Uf>@@ DQG ORZHU SRO\GLVSHUVLW\ LQGH[ RI ZDV V\QWKHVL]HG VHH 7DEOH f (OHPHQWDO DQDO\VLV IRU WKH SRO\PHUV DQG RWKHU FRPSRXQGV GLVFXVVHG WKURXJKRXW WKLV FKDSWHU DUH VKRZQ LQ 7DEOH )LJXUH VKRZV WKH *3& WUDFH IRU 333 1(WGSSIf>@ *3& WUDFHV IRU WKH RWKHU 3331(W SRO\PHUV DUH VLPLODU ZLWK UHWHQWLRQ WLPH DQG SHDN ZLGWK YDU\LQJ IRU PROHFXODU ZHLJKW DQG SRO\GLVSHUVLW\ UHVSHFWLYHO\ 6FDOH XS E\ D IDFWRU RI WR WLPHV WKH RULJLQDO VFDOH ZDV VXFFHVVIXO XVLQJ WKH 3G&(&GSSIf FDWDO\VW DV ZHOO DV SUHYHQWLRQ RI 3Gf FRQWDPLQDWLRQ 'DWD VKRZQ LQ 7DEOH IRU WKH 3G2$Ff SRO\PHUV ZDV WDNHQ IURP WKH GLVVHUWDWLRQ RI 'U 3HWHU %DODQGD 6XEVHTXHQW SRO\PHUL]DWLRQV FRQGXFWHG XVLQJ 3G2$Ff UHSURGXFHG WKLV GDWD ZLWKLQ H[SHULPHQWDO HUURUV ,W VKRXOG EH QRWHG WKDW WKH ORZ SRO\GLVSHUVLW\ IRXQG IRU WKH 3G&ELGSSIf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f YLD 6X]XNL SURWRFRO %RWK UHDFWLRQV ZHUH TXHQFKHG E\ SUHFLSLWDWLRQ LQWR

PAGE 46

3G&,GSSHf 3G&,GSSSf 3G&,GSSIf &O3G&O %RQG $QJOH r r r )LJXUH &O3G&O ERQG DQJOH IRU 3G&OGSSHf 3G&OGSSSf DQG 3G&OGSSIf FDWDO\VWV 0H2+ DIWHU KRXUV *3& UHVXOWV LQ FKORURIRUP YV 36 VWDQGDUGVf UHYHDOHG ORZ PROHFXODU ZHLJKW ROLJRPHUV 0Q J PROn PXOWLPRGDOf IRU WKH UHDFWLRQ XVLQJWKH GLEURPRQDWHG VSHFLHV >3331(W%Uf@ 7KH UHDFWLRQ XVLQJ WKH GLLRGRQDWHG UHDJHQW >3331(W,f>@@ UHDFKHG D 0Q J PROn ZLWK D FRQWLQXRXV SRO\PHULF GLVWULEXWLRQ 3XEOLVKHG UHVXOWV XVLQJ '%1(W LQ WKH UHDFWLRQ IRU KRXUV VKRZHG D 0Q J PRO IRU WKH UHVXOWLQJ SRO\PHU >3331(W%Uf>@@ 7KH HOHPHQWDO DQDO\VLV DQG *3& UHVXOWV DUH VXPPDUL]HG LQ 7DEOHV DQG UHVSHFWLYHO\ /RQJHU UHDFWLRQ WLPHV FRPSOHWH SRO\PHUL]DWLRQ VWRSSHG DIWHU KRXUVf ZLWK ',1(W >3331(W ,f>@ 0Q J PROn @ DSSURDFKHG WKH PROHFXODU ZHLJKW YDOXHV UHSRUWHG IRU 333 1(W%Uf>@ 7KH XVH RI ',1(W OHDGV WR WKH IRUPDWLRQ RI D SRO\PHU ZLWK VLPLODU PROHFXODU ZHLJKW SURSHUWLHV WR 3331(W%Uf>@ LQ D VKRUWHU DPRXQW RI WLPH 2QFH WKH SRO\PHU KDV UHDFKHG D FHUWDLQ PROHFXODU ZHLJKW LW EHJLQV WR SUHFLSLWDWH RXW RI VROXWLRQ VWRSSLQJ SRO\PHU JURZWK DQG QHJDWLQJ WKH DGYDQWDJHV RI WKH PRUH UHDFWLYH LRGLQH UHDJHQW DW ORQJHU UHDFWLRQ WLPHV

PAGE 47

,Q RUGHU WR JDLQ LQVLJKW LQWR D SRO\PHU WKDW PLPLFV WUXH 333 PRUH DFFXUDWHO\ 333%31(W>@ ZDV V\QWKHVL]HG VHH )LJXUH f 7KH ERURQLF HVWHU RI ELSKHQ\O ZDV FRXSOHG ZLWK '%1(W XVLQJ WKH SRO\PHUL]DWLRQ FRQGLWLRQV GHWHUPLQHG IRU 333 1(WGSSIf>@ >3G&KLGSSIf '0)))2 DQG 1D+&@ 'XULQJ WKH FRXUVH RI WKH SRO\PHUL]DWLRQ LW ZDV QRWHG WKDW WKH SRO\PHULF ROLJRPHULF PDWHULDOV EHLQJ IRUPHG ZHUH SUHFLSLWDWLQJ RXW RI VROXWLRQ PXFK HDUOLHU WKDQ IRU WKH 3331(W UHDFWLRQV 6XEVHTXHQW ZRUNXS UHYHDOHG RQO\ ORZ PROHFXODU ZHLJKW FRPSRQHQWV 0Q JPROf IRU WKH LVRODWHG SRO\PHU DV GHWHUPLQHG E\ *3& YHUVXV SRO\VW\UHQH VWDQGDUGV DQG D KLJK OHYHO bf RI EURPLQH HQGJURXSV DV GHWHFWHG E\ HOHPHQWDO DQDO\VLV 2QO\ b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

PAGE 48

)LJXUH *HO SHUPHDWLRQ FKURPDWRJUDP IRU 3331(WGSSIf>@ 7DEOH &DWDO\VW HIIHFW RQ WKH PROHFXODU ZHLJKW SURSHUWLHV RI 3331(WBSRO\PHUV FDWDO\VW UHDFWLRQ VROYHQW \LHOG &DOLEUDWLRQ PHWKRG NJ PROnO 03 NJ PROnO NJ PROnO 3G2$Ff 7+) b 36 SSSD 3G2$Ff '0) b 36 333 3G&OGSSIf 7+) b 36 333 3G2$Ff DFHWRQH b 36 333 *3& UHVXOWV LQ &+&, YV SRO\VW\UHQH VWDQGDUGV 3G2$Ff GDWD WDNHQ IURP 'U 3HWHU %DODQGD GLVVHUWDWLRQ 8 RI )ORULGD D 8QLYHUVDO FDOLEUDWLRQ XVLQJ YDOXHV GHULYHG IRU 333 LQ 7+)

PAGE 49

7DEOH (OHPHQWDO $QDO\VLV UHVXOWV IRU 333 PRQRPHUV DQG SRO\PHUV 6SHFLHV b& b+ b1 bO b%U $QDO &DOHG IRU 7KHR &+12, ',1(W ([S 7KHR B &L+1%U '%1(W ([S 7KHR &+12 333PRGHO f ([S 333PRGHO 7KHR &+R1%U ,' ([S 7KHR &+12% 3331(W GSSIf>@ ([S 3331(W 7KHR & +12%, %Uf>@ ([S 3331(W 7KHR &+12,2 ,f>@ ([S 3331(W 7KHR &+12,2 ,f>@ ([S 333%3 7KHR &+12 1(W>@ ([S &+12 3331(W 7KHR &+%U >@ ([S + 333%3 7KHR &+1%U 1(W >@ ([S

PAGE 50

7DEOH (IIHFW RI '%1(W RU ',1(W RQ WKH PROHFXODU ZHLJKW RI 3331(W SRO\PHUV SRO\PHU UHDFWLRQ VROYHQW UHDFWLRQ W\SH UHDFWLRQ WLPH KRXUVf 03 0M0Q 3331(W %Uf>@ GPIKR 6X]XNL 3331(W ,f>@ '0)+ 6X]XNL 3331(W ,f>@ '0)+2 6X]XNL 0ROHFXODU ZHLJKW YDOXHV DUH H[SUHVVHG LQ XQLWV RI NJ PRO *3& UHODWLYH WR SRO\VW\UHQH VWDQGDUGV )LJXUH (QYLVLRQHG ERURQLF UHDJHQWV IRU D PRUH VXEVWLWXWHG 3331(W SRO\PHU 3G2$Ff '0) KHDW )LJXUH 3G FDWDO\]HG FRXSOLQJ WR GLERURQLF UHDJHQWV IRU 6X]XNL FRXSOLQJV

PAGE 51

DQG WUDQVHVWHULILFDWLRQ ZLWK QHRSHQW\O JO\FRO %RWK DWWHPSWV ZHUH XQVXFFHVVIXO SRVVLEO\ FDXVHG E\ DQ LQWHUDFWLRQ RI WKH DPLQH JURXSV WR WKH WULPHWK\O ERUDWH KLQGHULQJ IRUPDWLRQ RI WKH QHZ SKHQ\OERURQ ERQG *ULJQDUG DQG OLWKLDWLRQ SURFHGXUHV ZHUH HIIHFWLYH DV HYLGHQFHG E\ D VXEVWDQWLDO DPRXQW RI GHKDORJHQDWHG PDWHULDO LQ WKH FUXGH LVRODWHG PDWHULDO )XWXUH ZRUN FRXOG H[SORUH XVLQJ D SDOODGLXP FDWDO\]HG UHDFWLRQ EHWZHHQ GL KDORJHQDWHG SKHQ\OHQHfV DQG GLERURQ SLQDFRO HVWHU VHH )LJXUH f WKDW KDV EHHQ VKRZQ WR HIIHFWLYHO\ SURGXFH ERURQLF UHDJHQWV IRU 6X]XNL UHDFWLRQV DV DQ DOWHUQDWLYH URXWH WR WKH GHVLUHG FRPSRXQG 3RO\PHU 4XDWHPL]DWLRQ 4XDWHPL]DWLRQ RI WKH DPLQH VLWHV IROORZHG SUHSDUDWLRQ RI WKH QHXWUDO SRO\PHUV 6\QWKHVLV RI SRO\>ELV^1 $$WULHWK\ODPPRQLXP-OR[DSURS\2OASKHQ\OHQHWII SKHQ\OHQH@ GLEURPLGH 3331(W>@f LV DFFRPSOLVKHG E\ KHDWLQJ WKH QHXWUDO SRO\PHU LQ D '062 7+) VROXWLRQ ZLWK EURPRHWKDQH IRU GD\V )LJXUH f n+ 105 LQGLFDWHV WKDW D KLJK GHJUHH RI WKH DPLQH VLWHV DUH TXDWHPL]HG bf (OHPHQWDO DQDO\VLV IRU EURPLQH FRQWHQW DOVR UHIOHFWV b TXDWHPL]DWLRQ VHH 7DEOH f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}>@ GLVSOD\HG H[FHOOHQW VROXELOLW\ LQ ERWK DFLGLF DQG QHXWUDO DTXHRXV PHGLD 6ROXWLRQV ZHUH VWDEOH RYHU WKH WLPH

PAGE 52

IUDPH RI GD\V ZLWK RQO\ PLQLPDO SUHFLSLWDWLRQ RI SRO\PHU IURP VROXWLRQ REVHUYHG RQ VDPSOHV VWRUHG RYHU D PRQWK )LJXUH 4XDWHPL]DWLRQ RI 3331(W 333%31(W>@ ZDV VXEMHFWHG WR WKH VDPH TXDWHPL]DWLRQ FRQGLWLRQV DV VKRZQ LQ )LJXUH &RPSOHWH TXDWHPL]DWLRQ RI WKLV PDWHULDO ZDV QRW DFKLHYHG DV WKH QHXWUDO PDWHULDO ZDV GLIILFXOW WR GLVVROYH LQ WKH TXDWHPL]DWLRQ PHGLD f+ 105 DQDO\VLV RI WKH PDWHULDO ZDV XQVXFFHVVIXO GXH WR WKH SRRU VROXELOLW\ LQ FRPPRQ GHXWHUDWHG VROYHQWV (OHPHQWDO DQDO\VLV 7DEOH f RI WKH ROLJRPHUV UHYHDOHG D ZHLJKW SHUFHQW RI EURPLQH 2I WKLV DPRXQW b RI EURPLQH LV GXH WR TXDWHPL]HG DPPRQLXP VLWHV DQG b LV LQKHUHQW IURP WKH SDUHQW 333%31(W>@ )XOO TXDWHPL]DWLRQ RI DOO DPLQH VLWHV ZRXOG UHTXLUH b EURPLQH 2YHUDOO WKLV LQGLFDWHV WKDW DSSUR[LPDWHO\ KDOI RI WKH DPLQH VLWHV ZHUH TXDWHPL]HG 7KH UHVXOWLQJ TXDWHPL]HG ROLJRPHUV ZHUH QR ORQJHU VROXEOH LQ &+&, RU 7+) EXW KDG UHDVRQDEOH VROXELOLW\ RQ WKH RUGHU RI [ r 0 EDVHG RQ UHSHDW XQLW 0:f LQ ZDUP DFHWRQLWULOH RU '062 &ORXG\ fVXVSHQVLRQVf LQ QHXWUDO + ZHUH IRUPHG LQ WKH 0 FRQFHQWUDWLRQ UDQJH 7KH SRO\PHU ZDV VROXEOH LQ ZDWHU RQO\ LI WKH S+ ZDV ORZHUHG WR DURXQG RU

PAGE 53

3K\VLFDO 3URSHUWLHV RI 333 7\SH 3RO\PHUV )RU RSWLFDO GLVSOD\ XVHV VXFK DV RUJDQLF OLJKW HPLWWLQJ GHYLFHV 2/('fVf HQYLVLRQHG IRU 3331(W>@ WKH WZR PRVW LPSRUWDQW SK\VLFDO SURSHUWLHV IRU WKH SRO\PHU DUH DEVRLSWLRQ DQG HPLVVLRQ ZDYHOHQJWKV DQG WKHUPDO VWDELOLW\ 7KH DEVRUSWLRQ DQG HPLVVLRQ ZDYHOHQJWKV ZLOO REYLRXVO\ FRQWURO WKH FRORU RI WKH GLVSOD\ GHYLFH DQG /('fV RSHUDWLQJ XQGHU D KLJK ELDV DUH OLPLWHG LQ OLIHWLPH E\ WKHUPDO DQG HOHFWULF ILHOG LQGXFHG GHJUDGDWLRQV 0DWHULDOV ZLWK ORZ EDUULHUV WR WKHUPDO GHJUDGDWLRQ DUH RI OLPLWHG XVH 7KH VROXWLRQ DEVRUEDQFH DQG HPLVVLRQ EHKDYLRU RI WKH QHZHVW 3331(W>@ DQG 3331(W>@ VDPSOHV PDWFK WKH GDWD UHSRUWHG IRU WKH LQLWLDO SRO\PHU VDPSOHV SUHSDUHG E\ 'U 3HWHU %DODQGD $EVRUSWLRQ VSHFWUD IRU WKH QHXWUDO SRO\PHU LQ 7+) SORW Ff QHXWUDO SRO\PHU LQ 0 +& SORW Ef DQG TXDWHPL]HG SRO\PHU LQ +2 SORW Df DUH UHSUHVHQWHG RQ WKH OHIW KDOI RI WKH JUDSK LQ )LJXUH ,QWHUHVWLQJO\ D VLJQLILFDQW EOXH VKLIWLQJ RI WKH VROXWLRQ DEVRLSWLRQ PD[LPXP RFFXUV IURP WKH QHXWUDO ;PD[ QPf WR TXDWHPL]HG $PD[ QPf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

PAGE 54

HPLVVLRQ EHWZHHQ WKH QHXWUDO SRO\PHU LQ 7+) SORW If QHXWUDO SRO\PHU LQ 0 +& SORW Gf DQG WKH TXDWHPL]HG SRO\PHU LQ + SORW Hf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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f WKH VLPLODULW\ LQ WKLQ ILOP DEVRUSWLRQ GDWD LQGLFDWHV WKDW WKH DONR[\DPLQH VLGH JURXSV DORQJ WKH EDFNERQH RI 3331(W>@ DUH GLVWXUELQJ WKH FRQMXJDWHG EDFNERQH SODQDULW\ YHU\ OLWWOH DOORZLQJ WKH FRQMXJDWHG EDFNERQH WR PDLQWDLQ D YHU\ ULJLG FRQIRUPDWLRQ

PAGE 55

:DYHOHQJWK )LJXUH 899LV (PLVVLRQ EHKDYLRU RI QHXWUDO DQG ZDWHU VROXEOH 3331(W Df 3331(W>@ LQ 7+) SORWV F DQG I Ef 3331(W>@ LQ 0 +& SORWV E DQG G Ff 3331(W>@ LQ + SORWV D DQG H )LJXUH WDNHQ IURP %DODQGD 3% 5DPH\ 0% 5H\QROGV -5 0FLFURPROHFXOHV 7KHUPDO DQDO\VLV E\ 7*$ XQGHU QLWURJHQ DWPRVSKHUHf )LJXUH f LQGLFDWHG DQ RQVHW IRU GHFRPSRVLWLRQ RYHU r& IRU 3331(W>@ DQG DW FD r& IRU 333 1(W>@ ZLWK D VPDOO DPRXQW RI ZDWHU ORVV DW ORZHU WHPSHUDWXUHVf )URP WKH SHUVSHFWLYH RI GHYLFH DSSOLFDWLRQV WKH PRVW LPSRUWDQW GHJUDGDWLRQ HYHQW LV WKH RQH ZKLFK RFFXUV ILUVW 7KH ILUVW GHJUDGDWLRQ HYHQW IRU ERWK SRO\PHUV ZDV GHWHUPLQHG WR EH VLGH FKDLQ FOHDYDJH LQFOXGLQJ WKH ORVV RI HWK\O EURPLGH IRU WKH TXDWHPL]HG VDPSOH 7KH 3/ ,QWHQVLW\ DXf

PAGE 56

)LJXUH 3KRWROXPLQHVFHQW VSHFWUXP RI 3331(W>@ LQ 7+) ZLWK QRUPDOL]HG DQG OLQHDU HPLVVLRQ VFDOH IDFW WKDW WKH WKHUPDO GHJUDGDWLRQ RI WKHVH DONR[\ VXEVWLWXWHG 333fV LV D UHODWLYHO\ FOHDQ SURFHVV PD\ SURYLGH D URXWH WR K\GUR[\ODWHG 333fV 6DPSOHV RI 3331(W>@ KHDWHG WR r IRU PLQ ZHUH QR ORQJHU VROXEOH LQ &+&, RU 7+) EXW GLG SRVVHVV EOXH SKRWROXPLQHVFHQFH ZKHQ H[SRVHG WR XOWUDYLROHW OLJKW 7UHDWPHQW RI 3331(W>@ ZLWK %% D UHDJHQW NQRZQ IRU LWV DELOLW\ WR FOHDYH DU\O HWKHUVf DOVR UHVXOWHG LQ D PDWHULDO LQVROXEOH LQ &+&, RU 7+) ZLWK WKH DERYH PHQWLRQHG HPLVVLRQ FKDUDFWHULVWLF &RQFOXVLRQV $Q LQWHUHVWLQJ ZDWHU VROXEOH SRO\"SKHQ\OHQHf 3331(W>@f KDV EHHQ V\QWKHVL]HG E\ D YDULHW\ RI PRGLILFDWLRQV RI 6X]XNL SRO\PHUL]DWLRQ WHFKQLTXHV 7KH XVH

PAGE 57

)LJXUH 7*$ WKHUPRJUDPV IRU QHXWUDO DQG ZDWHU VROXEOH 3331(W XQGHU 1 Df 3331(W>@ Ef 3331(W>@ RI 3G&OGSSIf DV FDWDO\VW KDV LQFUHDVHG V\QWKHWLF \LHOG WR WKH SRLQW ZKHUHE\ D UHODWLYHO\ KLJK PROHFXODU ZHLJKW SRO\PHU ZLWK ORZ SRO\GLVSHUVLW\ FDQ EH PDGH ZLWKRXW WKH H[WUD VWHSV RI fFOHDQLQJf SUHFLSLWDWHG 3G RXW RI WKH SRO\PHU 7KH 3G&OGSSIf FDWDO\VW ZDV DOVR VXFFHVVIXO LQ DOORZLQJ SRO\PHUL]DWLRQ VFDOHXS WR WKH PXOWLJUDP OHYHO )RU WKLV V\VWHP PD[LPXP FKDLQ JURZWK LV OLPLWHG E\ WKH SUHFLSLWDWLRQ RI ORQJHU SRO\PHU FKDLQV GXULQJ WKH FRDUVH RI WKH UHDFWLRQ

PAGE 58

,QFUHDVLQJ WKH QXPEHU RI XQVXEVWLWXWHG SKHQ\O ULQJV LQ WKH SRO\PHU EDFNERQH 333%31(W>@ ORZHUV PROHFXODU ZHLJKW GXH WR SUHFLSLWDWLRQ RI WKH SRO\PHU RXW RI WKH UHDFWLRQ SULRU WR KLJK FRQYHUVLRQV 6XEVHTXHQW RSWLFDO DEVRUSWLRQ GDWD RQ WKLQ ILOP FDVWLQJV RI OHVV VXEVWLWXWHG VDPSOHV WR WKH PRUH VXEVWLWXWHG 3331(W>@ KHOSV VXSSRUW WKH WKHRU\ WKDW WKH DONR[\DPLQH VLGH JURXSV RQ 3331(W>@ KDYH PLQLPDO LQWHUDFWLRQV WKDW DIIHFW EDFNERQH SODQDULW\

PAGE 59

&+$37(5 &$7,21,& 32/@ DUH W\SLFDOO\ VWURQJ EOXH HPLWWLQJ SRO\PHUV LW LV GHVLUDEOH WR KDYH VWUXFWXUDOO\ VLPLODU PDWHULDOV ZLWK D UDQJH RI HPLVVLRQ ZDYHOHQJWKV 2QH DSSURDFK WR fWXQHf WKH HPLVVLRQ ZDYHOHQJWK RI D SRO\PHU LV WR FKHPLFDOO\ FKDQJH WKH PDNHXS RI WKH EDFNERQH VWUXFWXUH %\ LQFRUSRUDWLRQ RI PRUH HOHFWURQ ULFK PRLHWLHV LQWR WKH UHSHDW XQLW VWUXFWXUH WKH KLJKHVW RFFXSLHG PROHFXODU RUELWDO +202f WR ORZHVW RFFXSLHG PROHFXODU RUELWDO /802f HOHFWURQLF EDQGJDS LV ORZHUHG 6SHFLILFDOO\ HOHFWURQ ULFK VSHFLHV UDLVH WKH +202 DQG KDYH OLWWOH HIIHFW RQ WKH /802 WKHUHE\ GHFUHDVLQJ EDQGJDS RYHUDOO $V WKH EDQGJDS LV ORZHUHG WKH HQHUJ\ QHHGHG WR H[FLWH DQ HOHFWURQ LQWR WKH /802 LV UHGXFHG DQG WKHUHIRUH WKH HQHUJ\ ZDYHOHQJWKf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fSDUHQWf 3331(W>@ SRO\PHU GLVFXVVHG LQ &KDSWHU RI WKLV GLVVHUWDWLRQ

PAGE 60

(DUO\ 6\QWKHWLF $WWHPSWV $Q HDUO\ DSSURDFK WR LQFRUSRUDWH WKLRSKHQH XQLWV LQWR D SRO\SSKHQ\OHQHFR WKLRSKHQHf EDFNERQH ZDV EDVHG RQ D SRO\ GLNHWRQHf SUHSDUHG E\ D 6WHWWHU UHDFWLRQ WKDW ZDV WUHDWHG ZLWK /DZHVVRQfV UHDJHQW WR LQFRUSRUDWH VXOIXU LQWR WKH EDFNERQH )LJXUH ODf 7KH KDUVK FRQGLWLRQV UHTXLUHG ZDV D PDMRU IODZ LQ WKLV DSSURDFK DV FURVVOLQNLQJ ZDV SURPRWHG &]HUZLQVNL HW DO XVHG D *ULJQDUG FRXSOLQJ EHWZHHQ SGLEURPREHQ]HQH DQG GLEURPRWKLRSKHQH LQ YDULRXV IHHG UDWLRV WR LQFRUSRUDWH WKLRSKHQH DQG SKHQ\OHQH XQLWV LQWR WKH EDFNERQH )LJXUH OEf $OWHUQDWLQJ FRSRO\PHUV FRQWDLQLQJ DU\OHQH DQG ELWKLRSKHQH UHSHDW XQLWV KDYH EHHQ V\QWKHVL]HG YLD HOHFWURFKHPLFDO SRO\PHUL]DWLRQ RI OGLWKLHQ\ODU\OHQHV )LJXUH OFff 7KH HOHFWURFKHPLFDO SRO\PHUL]DWLRQV IRUP LQVROXEOH ILOPV RQ FRQGXFWLYH VXEVWUDWHV OLPLWLQJ SRO\PHU SURFHVVLQJ WR WKH LQLWLDO GHSRVLWLRQ 3HOWHU HW DO XVHG ]LQF FKORULGH WR PHW£ODWH WKH DQG f SRVLWLRQV RI OGL WKLHQ\OfSKHQ\OHQH DQG UHDFWHG WKH LQWHUPHGLDWH ZLWK OGLEURPRGLVXEVWLWXWHG EHQ]HQHV YLD D *ULJQDUG FRXSOLQJ )LJXUH OGf 7KH SRO\PHUV FRXOG EH GRSHG E\ IHUULF FKORULGH RU LRGLQH WR FRQGXFWLYLWLHV EHWZHHQ n DQG FPn 'U )XSLQJ
PAGE 61

4 1D&1 4 + 1D&1 /DZHVVRQnV f [ %UnA?6A%U \ %Uf§A A %U 0J 1LDFDFf [PX 5 HT %U 3Gf 0 =Q&, 6Q0H 5 + DON\O DONR[\ IXQFWLRQDO JURXS 5 &O=Q R B =Q&, 5 5 DON\O DONR[\ QLWUR )LJXUH /LWHUDWXUH H[DPSOHV RI SKHQ\OHQHFRWKLRSKHQH W\SH SRO\PHUV 3Gf ;f§5f§; %X6Qf§5n6Q%X +Q ; %U 6&)L &2&, 5 5n DURPDWLF YLQ\O KHWHURF\FOLF HWF )LJXUH *HQHUDO VFKHPH IRU WKH 6WLOOH SRO\PHUL]DWLRQ

PAGE 62

ZHLJKW RI FD J PRO YHUVXV SRO\VW\UHQH VWDQGDUGV 7KLV FODVV RI SRO\PHU SRVVHVVHV D EDQGJDS RI FD H9 QPf IDOOLQJ EHWZHHQ WKDW RI SRO\"SKHQ\OHQHf H9 QPf DQG SRO\WKLRSKHQH H9 QPf $Q HPLVVLRQ DW QP ZDV SUHVHQW LQ SKRWROXPLQHVFHQFH VWXGLHV FRQGXFWHG LQ 7+) ZKHQ WKH SRO\PHU VROXWLRQ ZDV H[FLWHG ZLWK D ZDYHOHQJWK RI OLJKW FRUUHVSRQGLQJ WR LWV DEVRUSWLRQ PD[LPXP ZKHQ WKH SRO\PHU VROXWLRQ ZDV H[FLWHG ZLWK D ZDYHOHQJWK RI OLJKW FRUUHVSRQGLQJ WR LWV DEVRUSWLRQ PD[LPXP 2SWLPL]DWLRQ RI WKH 6WLOOH &RXSOLQJ 3RO\PHUL]DWLRQ ,Q RUGHU WR PD[LPL]H WKH HIILFDF\ RI WKH 6WLOOH UHDFWLRQ IRU SRO\PHUL]DWLRQV D PRUH GHWDLOHG VWXG\ E\
PAGE 63

7DEOH 6WUXFWXUHV RI WKH RUJDQRKDOLGHV DQG WULIODWHV IRU WKH 6WLOOH UHDFWLRQV 5 5 &RPSRXQG 5 ; 2&+ RFK %U RFK 27I &+ &+ %U &+ 27I 2&+ 27I QR VXEVWLWXWLRQ 27I r7DNHQ IURP %DR = :DLNLQ &
PAGE 64

UDWLR WR DFFRXQW IRU UHGXFWLRQ RI WKH SDOODGLXP ,,f FDWDO\VW WR WKH DFWLYH SDOODGLXP f VSHFLHV E\ WKH RUJDQRWLQ VSHFLHV LQFUHDVHG PROHFXODU ZHLJKWV 7KH RUJDQRWLQ FRPSRXQG ZRXOG EH XVHG LQ D HTXLYDOHQW DPRXQW FRPSDUHG WR HTXLYDOHQW RI RUJDQRKDOLGH 5 &Q+QL RU 2&Q+QO 7DNHQ IURP %DR = :DLNLQ &
PAGE 65

1XPEHU DYHUDJH PROHFXODU ZHLJKWV RI XS WR J PROn ZHUH DFKLHYHG IRU WKH 337 SRO\PHUV XVLQJ HTXLYDOHQW RI OGLLRGRGLRFW\OEHQ]HQH HTXLYDOHQWV RI ELVWULEXW\OVWDQQ\OfWKLRSKHQH DQG PROb 3G&O33Kf FDWDO\VW LQ r& '0) IRU RQH ZHHN 2I DOO RUJDQRWLQ PRQRPHUV VWXGLHG WKH ELVWULEXW\OVWDQQ\OfWKLRSKHQH VHH 7DEOH f ZDV WKH PRVW UHDFWLYH DV WKH HOHFWURQ GRQDWLQJ SURSHUW\ RI WKH VXOIXU DWRP PD\ DFFHOHUDWH WKH WUDQVPHWDODWLRQ VWHS ZKLFK KDV EHHQ SURSRVHG WR EH WKH UDWH GHWHUPLQLQJ VWHS IRU SDOODGLXPFDWDO\]HG FURVV FRXSOLQJ UHDFWLRQV $Q DOWHUQDWH WLQ UHDJHQW QRW XVHG LQ 9L9GLHWK\ODPLQR@OR[DSURS\OfOGLLRGREHQ]HQH ',1(Wf>VHH &KDSWHU @ ,I VXFFHVVIXO D QHXWUDO SRO\"SKHQ\OHQHFWKLRSKHQHf ZLWK DONR[\DPLQH VLGH FKDLQV RQ WKH SKHQ\OHQH XQLWV ZRXOG EH FUHDWHG WKDW VKRXOG EHFRPH ZDWHU VROXEOH XSRQ WUHDWPHQW ZLWK HWK\O EURPLGH 7KH VROXWLRQ HPLVVLRQ RI WKLV SRO\PHU VKRXOG IDOO LQ WKH JUHHQ WR \HOORZ YLVLEOH ZDYHOHQJWK UDQJH E\ FRPSDULVRQ WR OLWHUDWXUH YDOXHV 8VLQJ WKH LQVLJKWV LQWR WKH 6WLOOH FRXSOLQJ IRXQG E\ L9$

PAGE 66

GLHWK\ODPLQRfOR[DSURS\O@OSKHQ\OHQH`WIUWKLHQ\OHQHf 3371(Wf ZKLFK LV HDVLO\ FRQYHUWHG WR WKH TXDWHUQDU\ DPPRQLXP VDOW SRO\^ELV>$9$ WULHWK\ODPPRQLXPfOR[DSURS\O@OSKHQ\OHQHDLWKLHQ\OHQH` GLEURPLGH 337 1(f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fOGLLRGREHQ]HQH ',1(Wf )LJXUH f DQG ELVWULPHWK\OVWDQQ\OfWKLRSKHQH f RU WKLRSKHQH GLERURQLF DFLG f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fWKLRSKHQH f E\ OLWHUDWXUH PHWKRGRORJ\ LV RXWOLQHG LQ )LJXUH 7KLRSKHQH ZDV WUHDWHG ZLWK HTXLYDOHQWV RI QEXW\OOLWKLXP DQG UHIOX[HG LQ D KH[DQH 70('$ VROXWLRQ IRU PLQXWHV FRROHG WR r& LQ DQ LFH EDWK DQG TXHQFKHG ZLWK HTXLYDOHQWV RI WULPHWK\OVWDQQ\O FKORULGH $IWHU

PAGE 67

VWLUULQJ RYHUQLJKW DTXHRXV H[WUDFWLRQ IROORZHG E\ UHPRYDO RI KH[DQH XQGHU UHGXFHG SUHVVXUH UHYHDOHG D VOLJKWO\ EURZQ VROLG 7KH VWDQQ\ODWHG FRPSRXQG ZDV GLVWLOOHG XQGHU YDFXXP DQG UHFU\VWDOOL]HG WZLFH IURP SHQWDQH WR \LHOG ZKLWH FU\VWDOV LQ b \LHOG 7KH FRUUHVSRQGLQJ 6X]XNL UHDJHQW WKLRSKHQH GLERURQLF DFLG f ZDV SUHSDUHG E\ WUHDWLQJ GLEURPRWKLRSKHQH ZLWK HTXLYDOHQWV RI 0J IROORZHG E\ TXHQFKLQJ ZLWK DQ H[FHVV RI GU\ WULPHWK\OERUDWH 7KH UHDFWLRQ ZDV VWLUUHG RYHUQLJKW DQG 0 +& ZDV DGGHG WR SURWRQDWH WKH GLDFLG DQG GLVVROYH DOO PDJQHVLXP VDOWV $IWHU DQ DTXHRXV (W H[WUDFWLRQ WKH FUXGH SURGXFW ZDV SUHFLSLWDWHG LQWR 0 +& FROOHFWHG DQG UHFU\VWDOOL]HG IURP KRW + $ b \LHOG RI ZKLWH FU\VWDOV ZDV UHFRYHUHG DQG GULHG LQ YDFXR DW r& IRU KRXUV $V LV WKH FDVH ZLWK ERURQLF DFLGV SXULILFDWLRQ DQG GU\LQJ ZHUH VLPSOLILHG E\ UHDFWLQJ WKH GLDFLG ZLWK QHRSHQW\O JO\FRO LQ UHIOX[LQJ EHQ]HQH LQ D WUDQVHVWHULILFDWLRQ PDQQHU WR SURGXFH WKH WKLRSKHQH GLERURQDWH HVWHU f DV ZKLWH FU\VWDOV LQ b \LHOG DV RXWOLQHG LQ )LJXUH HT Q%X/L 70('$ KH[DQH UHIOX[ K HT 0H6Q&, 57 RYHUQLJKW )LJXUH 6\QWKHVLV RI ELVWULPHWK\OVWDQQ\OfWKLRSKHQH 'XH WR WKH ODFN RI OLWHUDWXUH DWWHPSWV DW SRO\PHUL]LQJ D WKLRSKHQH GLERURQLF DFLG RU HVWHU D WHVW FRXSOLQJ SURFHGXUH ZDV FDUULHG RXW WR GHWHUPLQH LI WKH UHDJHQW ZRXOG FRXSOH EHIRUH GHJUDGDWLRQ $ VLPSOH WKUHH FRPSRQHQW ULQJ V\VWHP ZDV FKRVHQ LQVWHDG RI WHVW SRO\PHUL]DWLRQV IRU WKH VWXG\ VLQFH WRR PDQ\ IDFWRUV DUH SUHVHQW LQ SRO\PHUL]DWLRQV

PAGE 68

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f DQG 3G&EGSSIf PRObf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f KR 2+ % ? 7+) 2+ b b )LJXUH 6\QWKHVLV RI WKLRSKHQH GLERURQDWH HVWHU

PAGE 69

3G&,GSSI 1D+& VROYHQW WHPS PHWKRG )LJXUH 7HVW FRXSOLQJ UHDFWLRQ RI WKLRSKHQH GLERURQDWH HVWHU DQG EURPRWROXHQH 7HVW UHDFWLRQV ZHUH PRQLWRUHG E\ WKLQ OD\HU FKURPDWRJUDSK\ WR FKHFN IRU WKH FRQVXPSWLRQ RI PROHFXOH DQG EURPRWROXHQH DORQJ ZLWK WKH DSSHDUDQFH RI QHZ FRPSRXQG VSRWV 5HDFWLRQV ZKLFK GLVSOD\HG SRVLWLYH 7/& UHVXOWV ZHUH ZRUNHG XS LVRODWLQJ WKH RUJDQLF SURGXFWV 6XEVHTXHQWO\ WKH PDWHULDO ZDV DQDO\]HG E\ JDV FKURPDWRJUDSK\PDVV VSHFWURPHWU\ *&06f WR GHWHUPLQH FRPSRVLWLRQ 7DEOH OLVWV WKH YDULRXV UHDFWLRQ FRPELQDWLRQV DQG UHVXOWV 6XUSULVLQJO\ FRXSOLQJ WR DQ\ VLJQLILFDQW OHYHO GRHV QRW RFFXU LQ 7+) 7\SLFDOO\ HYHQ LI 7+) SURYHV WR EH D SRRU VROYHQW IRU D 6X]XNL FRXSOLQJ WKH UHDFWLRQ ZLOO SURFHHG WR WKH b UDQJH *&06 SHDNV ZHUH DVVLJQDEOH RQO\ WR WKH VWDUWLQJ PDWHULDOV ZLWK D YHU\ VPDOO SHUFHQW bf RI PRQRVXEVWLWXWHG WKLRSKHQH SUHVHQW XSRQ VORZ DGGLWLRQ RI WKH ERURQDWH HVWHU ,W ZDV K\SRWKHVL]HG WKDW 7+) PD\ EH GHJUDGLQJ WKH UHDFWLYH WKLRSKHQH ERURQDWH HVWHU 7R KHOS GHWHUPLQH LI WKLV ZDV WKH FDVH D VPDOO VDPSOH RI FRPSRXQG ZDV SODFHG LQ 7+) ZLWK FDWDO\VW DQG 7+) RU '0) DQG WKH FRUUHFW UDWLR RI ZDWHUf ZLWKRXW EURPRWROXHQH DQG KHDWHG WR r& IRU KRXUV 7KH fUHDFWLRQVf ZHUH VWRSSHG DQG DQDO\]HG E\ *&06 %RWK UHYHDOHG WKH SHDN DVVLJQDEOH WR FRPSRXQG ZLWK QR GHJUDGDWLRQ SURGXFWV HYLGHQW )URP WKHVH UHVXOWV LW LV HYLGHQW WKDW 7+) DQG '0) GR QRW KDYH DQ\ GHJUDGDWLRQ HIIHFWV RQ WKH ERURQDWH HVWHU 7KH XVH RI WROXHQH DV D KLJKHU ERLOLQJ VROYHQW GLG QRW SURPRWH WKH UHDFWLRQ DQG *&06 UHYHDOHG KLJKHU OHYHOV RI GHJUDGDWLRQ

PAGE 70

SURGXFWV VXFK DV WKLRSKHQH DQG LWV PRQRERURQDWH HVWHU DV D UHVXOW RI WKH KLJKHU WHPSHUDWXUHV 7DEOH *&06 UHVXOWV RI 6X]XNL FRXSOLQJ RI WKLRSKHQH GLERURQDWH HVWHU DQG EURPRWROXHQH 6ROYHQW 7HPS &DWDO\VW 0HWKRG 5HVXOW 7+) 57 3G&OGSSI SRW 60 7+) UHIOX[ 3G&OGSSI SRW 60 GHJUDGDWLRQ 7ROXHQH UHIOX[ 3G&OGSSI SRW 60 ODUJH GHJUDGDWLRQ 7+) UHIOX[ 3G&OGSSI GURS ZLVH ORZ b PRQR '0) 57 3G&OGSSI SRW ORZ b PRQR 60 '0) r& 3G&OGSSI SRW 3URGXFW b '0) r& 3G&OGSSI GURSZLVH 3URGXFW b '0) r& 3G2$Ff GURSZLVH 3URGXFW b 57 5RRP 7HPSHUDWXUH a 8&f 60 6WDUWLQJ 0DWHULDOV &RPSRXQG DQG EURPRWROXHQHf 0RQR 2QH WRO\O XQLW FRXSOHG WR WKLRSKHQH 7KH FRXSOLQJ ZDV VXFFHVVIXO LQ DOO FDVHV LQ ZKLFK '0) DW HOHYDWHG WHPSHUDWXUHV ZDV XVHG 7KH DELOLW\ RI '0) WR FRRUGLQDWH WR WKH FDWDO\VW DQG LQFUHDVH FDWDO\WLF DFWLYLW\ LV EHOLHYHG WR DFFRXQW IRU WKH VXFFHVV RI XVLQJ WKLV VROYHQW LQ WKH UHDFWLRQ *&06 UHYHDOHG JRRG \LHOGV RI SURGXFW IRU DOO '0) UHDFWLRQV DW r& ZLWK H[FHOOHQW \LHOGV

PAGE 71

IRU FDVHV LQ ZKLFK WKH ERURQDWH HVWHU ZDV DGGHG GURSZLVH $V DQ DGGLWLRQDO WHVW WKH OHVV UHDFWLYH 3G2$Ff FDWDO\VW ZDV XVHG DQG \LHOGV IRU WKH UHDFWLRQ ZHUH DV KLJK DV WKRVH IRU WKH 3G&ELGSSIf 7KH DELOLW\ RI 3G2$Ff WR EH XVHG LQ WKH FRXSOLQJ LV LPSRUWDQW EHFDXVH WKH FDWDO\VW LV RQH RI WKH OHDVW H[SHQVLYH 3G FDWDO\VWV )RU SRO\PHUL]DWLRQV XVLQJ FRPSRXQG WKH WHVW UHDFWLRQV LQGLFDWH WKDW XVLQJ '0) DW r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fOR[DSURS\O@OSKHQ\OHQH`DIWKLHQ\OHQHf 3371(f LV GHSLFWHG LQ )LJXUH *HO SHUPHDWLRQ FKURPDWRJUDSK\ *3&f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f

PAGE 72

',1(W 3ROYPHU 7LPH 0HWKRG 3371(Wf >@ K SRW 3371(Wf >@ K SRW 3371(Wf >@ K SRW 3371(WGURSf >@ K GURSZLVH )LJXUH 6WLOOH FRXSOLQJ SRO\PHUL]DWLRQ VFKHPH IRU 3371(W 5HDFWLRQV ZHUH FRQGXFWHG XQGHU YDULHG FRQGLWLRQV WR GHWHUPLQH WKH RSWLPDO QHHGHG WR DFKLHYH WKH KLJKHVW PROHFXODU ZHLJKW SRVVLEOH IRU 3371( 7KH ILUVW VHW RI UHDFWLRQV ZHUH HDUQHG RXW DV RQH SRW V\QWKHVHV ZKHUH WKH VWDQQ\ODWHG FRPSRXQG ',1(W DQG '0) ZHUH PL[HG WRJHWKHU DQG KHDWHG WR r& 3G&O33Kf ZDV WKHQ DGGHG LQ RQH SRUWLRQ LQ D FDWDO\WLF DPRXQW WR WKH UHDFWLRQ IODVN 3371(Wf>@ DQG 3371(Wf>@ ZHUH V\QWKHVL]HG ZLWK DQG KRXU UHDFWLRQ WLPHV IROORZHG E\ SUHFLSLWDWLRQ LQWR 0H2+ 'XULQJ WKH SRO\PHUL]DWLRQ SRO\PHU ZDV VHHQ WR SUHFLSLWDWH RXW DQG FRDW WKH UHDFWRU 3371(Wf>@ ZDV FROOHFWHG LQb \LHOG ZLWK D 0Q RI J PROnZKLOH 3371(Wf>@ ZDV FROOHFWHG LQ b \LHOG ZLWK D 0Q RI J PRO *3& YHUVXV 36 VWDQGDUGVfVHH 7DEOH f 3RO\GLVSHUVLWLHV RI ZHUH IRXQG IRU ERWK EXW ZLWK WKH H[WHQVLYH IUDFWLRQDWLRQ GXULQJ SXULILFDWLRQ WKLV YDOXH LV QRW LQGLFDWLYH RI WKH LQLWLDO SRO\PHUL]DWLRQ 'RXEOLQJ WKH UHDFWLRQ WLPH OHDG WR D PRGHVW LPSURYHPHQWV LQ ERWK

PAGE 73

\LHOG DQG 0Q ZKLOH LQFUHDVLQJ WKH UHDFWLRQ WLPH WR GD\V LQ 3371(Wf>@ OHG WR QR DSSUHFLDEOH PROHFXODU ZHLJKW HQKDQFHPHQW 0Q RI J PROf /DWHU H[SHULPHQWV ZHUH ILQH WXQHG WR DFFRXQW IRU WKH SRVVLEOH GHJUDGDWLRQ RI WKH ELVWULPHWK\OVWDQQ\OfWKLRSKHQH ZKHQ H[SRVHG WR HOHYDWHG WHPSHUDWXUHV LQ WKH UHDFWLRQ PHGLXP 3371(WGURSf>@ ZDV V\QWKHVL]HG E\ VORZ GURSZLVH DGGLWLRQ RI WR D VROXWLRQ RI FDWDO\VW ',1(W DQG '0) YLD DQ DGGLWLRQ IXQQHO RYHU WKH FRXUVH RI KRXUV DQG DOORZHG WR UXQ IRU KRXUV 7KH UHDFWLRQ ZDV SUHFLSLWDWHG LQWR 0H2+ WKH FUXGH SRO\PHU UHFRYHUHG E\ ILOWUDWLRQ IROORZHG E\ H[WUDFWLRQ ZLWK 0H2+ DQG DFHWRQH IRU KRXUV HDFK DQG ILQDOO\ FROOHFWHG E\ H[WUDFWLRQ ZLWK FKORURIRUP YLD 6R[KOHW H[WUDFWRUf 7DEOH *HO SHUPHDWLRQ FKURPDWRJUDSK\ UHVXOWV IRU 6WLOOH FRXSOLQJ RI 3371(W SRO\PHU UHDFWLRQ VROYHQW UHDFWLRQ W\SH UHDFWLRQ WLPH KRXUVf NJ PRE 03 NJ PRE NJ PROn 3371(W '0) 6WLOOH f>@ 3371(W '0) 6WLOOH f>@ 3371(W '0) 6WLOOH f>@ 3371(W '0) 6WLOOH GURSf>@ GURSZLVHf *3& UHVXOWV LQ 7+) YV SRO\VW\UHQH VWDQGDUGV 7KH FKORURIRUP VROXEOH IUDFWLRQ FRQVWLWXWHG DQ b \LHOG DQG f+ DQG O& 105 DQDO\VLV JDYH H[SHFWHG VKLIW YDOXHV ZLWK WKH SURWRQ SHDNV DSSHDULQJ DV EURDG PXOWLSOHWV ZLWKRXW GHILQHG VSOLWWLQJ IRU DOO SRO\PHULF PDWHULDOV UHFRYHUHG VHH )LJXUH f 7KLV SRO\PHU H[KLELWV D 0Q RI J PROn *3& YHUVXV 36 VWDQGDUGVf 7KLV PHWKRGRORJ\

PAGE 74

7DEOH (OHPHQWDO $QDO\VLV UHVXOWV IRU 337 PRQRPHUV DQG SRO\PHUV 6SHFLHV b& b+ b1 b, b%U $QDO &DOHG IRU &RPSRXQG 7KHR &LR+L66Q ([S &RPSRXQG 7KHR FKEV ([S 3371(W 7KHR &+126, f>@ ([S 3371(W 7KHR &+126, f>@ ([S 3371(W 7KHR &+16,RR f>@ ([S 3371(W 7KHR &+16,RRR GURSf>@ ([S 7KHR &+16,RR 3371(W f>@ n &+%U ([S 3371(W 7KHR &+16,RR &+%U GURSf>@ ([S 3371(W 7KHR FKQRV 6X]f>@ ([S SURGXFHG D SRO\PHU ZLWK WKH ORZHVW SHUFHQW RI KDORJHQWDWHG HQGJURXSVZHLJKW b, DSSUR[LPDWHV D GHJUHH RI SRO\PHUL]DWLRQ FRUUHVSRQGLQJ WR ULQJVf DQG KLJKHVW

PAGE 75

PROHFXODU ZHLJKW E\ *3& RI DOO WULDOV 6ORZ DGGLWLRQ RI WKH PRUH UHDFWLYH WLQ FRPSRXQG DOORZV IRU LPPHGLDWH FRXSOLQJ RI WKH WKLRSKHQH WR ',1(W 7KLV OLPLWV WKH H[SRVXUH RI WKH VWDQQ\ODWHG FRPSRXQG WR WKH HOHYDWHG WHPSHUDWXUHV DQG ORZHUV WKH FKDQFH RI GHVWUR\LQJ WKH PDVV EDODQFH OHDGLQJ WR HQGFDSSLQJ RI WKH SRO\PHU FKDLQV ZLWK WKLRSKHQH RU FRPSOHWHO\ GHVWDQQ\ODWLQJ WKH WKLRSKHQH 7KLV PHWKRG OHG WR WKH KLJKHVW GHJUHH RI SRO\PHUL]DWLRQ IRU WKH 337nV SUHSDUHG ,6& = 6 ,W 6 ,, SSr )LJXUH n+ DQG O& 105 VSHFWUD RI 3371(W>@

PAGE 76

7KH QH[W V\QWKHWLF SURJUHVVLRQ DIWHU FRQILUPDWLRQ WKDW D EDVH VHW RI 3371( SRO\PHUV KDG EHHQ FUHDWHG ZDV WR WU\ WKH 6X]XNL FRXSOLQJ PHWKRGRORJ\ DV RXWOLQHG LQ )LJXUH &RPSRXQG ZDV DGGHG GURSZLVH WR D VWLUUHG VROXWLRQ RI ',1(W 3G&)LGSSIf DQG 1D+& LQ D '0) +2 VROYHQW VROXWLRQ DW r& $IWHU GD\V WKH UHDFWLRQ ZDV SUHFLSLWDWHG LQWR 0H2+ WKH FUXGH SRO\PHU UHFRYHUHG E\ ILOWUDWLRQ IROORZHG E\ H[WUDFWLRQ ZLWK 0H2+ DQG DFHWRQH IRU KRXUV HDFK DQG ILQDOO\ FROOHFWHG E\ H[WUDFWLRQ ZLWK FKORURIRUP YLD 6R[KOHW H[WUDFWRUf 7KH PDWHULDO 3371(W6X]f>@ ZDV UHFRYHUHG LQ b \LHOG )LJXUH 6\QWKHVLV RI 3371(W>@ YLD 6X]XNL FRXSOLQJ SRO\PHUL]DWLRQ (OHPHQWDO DQDO\VLV RI WKH SRO\PHU VHH 7DEOH f LQLWLDOO\ LQGLFDWHG D SRVVLEOH KLJK PROHFXODU ZHLJKW SRO\PHU ZLWK RQO\ b E\ ZHLJKW LRGLQH IRXQG LQ WKH VDPSOH KRZHYHU *3& WULDOV LQGLFDWHG YHU\ ORZ PROHFXODU ZHLJKW ROLJRPHULF VSHFLHV 899LV DEVRUSWLRQ GDWD VKRZHG D SHDN ;PD[ QP VRPH WHQ QDQRPHWHUV KLJKHU LQ ZDYHOHQJWK WKDQ WKH ZHOO DQDO\]HG PDWHULDOV IURP WKH 6WLOOH SRO\PHUL]DWLRQ VHH 3K\VLFDO 3URSHUWLHV

PAGE 77

VHFWLRQf 7KLV HYLGHQFH VXSSRUWV WKH FRQFOXVLRQ WKDW WKH JURZLQJ FKDLQV LQ WKH 6X]XNL UHDFWLRQ DUH EHLQJ WHUPLQDWHG E\ K\GURO\VLV RI WKH WHUPLQDO ERURQDWH IXQFWLRQDOLWLHV /RZHU PROHFXODU ZHLJKW VSHFLHV DQG VWDUWLQJ PDWHULDOV ZLWK LRGLQH JURXSV SUHVHQW ZHUH UHPRYHG E\ WKH H[WHQVLYH H[WUDFWLRQV SHUIRUPHG WKXV DFFRXQWLQJ IRU WKH ORZ b, 8QIRUWXQDWHO\ WKH 6X]XNL UHDFWLRQ IRU WKLRSKHQH ERURQDWHV LV QRW DSSOLFDEOH WR SRO\PHUL]DWLRQV GXH WR WKH HDVH RI K\GURO\VLV RI WKH ERURQDWH 7KH 6X]XNL W\SH UHDJHQWV DQG WHFKQLTXHV ZRXOG EH JRRG FDQGLGDWHV IRU V\QWKHVLV RI VPDOOHU WR ULQJ FRPSRXQGV DV HYLGHQFHG E\ WKH VXFFHVVIXO WHVW UHDFWLRQV 3RO\PHU 4XDWHPL]DWLRQ &DWLRQLF ZDWHU VROXEOH SRO\PHUV DUH HDVLO\ IRUPHG IURP WKH QHXWUDO 3371(W E\ TXDWHPL]DWLRQ ZLWK EURPRHWKDQH LQ 7+) DV VKRZQ LQ )LJXUH 7KH TXDWHPL]HG SRO\PHU 3371( ZDV SUHFLSLWDWHG LQWR DFHWRQH FROOHFWHG DQG GULHG DW r& XQGHU YDFXXP 7DEOH VKRZV WKH HOHPHQWDO DQDO\VLV UHVXOWV IRU 3371(Wf>@ DQG 3371(WGURSf>@ ZKLFK DUH WKH TXDWHPL]HG IRUPV RI 3371(Wf>@ DQG 3371(WGURSf>@ UHVSHFWLYHO\ 7KH UHVXOWLQJ SRO\PHUV DUH VROXEOH LQ DFLGLF VROXWLRQ DQG S+ ZDWHU 7KH TXDWHPL]DWLRQ HIILFLHQF\ DV GHWHUPLQHG E\ f+ 105 LQWHJUDWLRQ FRPSDULVRQ RI WKH LQWHJUDO YDOXH RI WKH WHUPLQDO VLGH FKDLQ SURWRQV1 &+&+r WR WKDW RI WKH 2&+"r SURWRQV > IRU b TXDWHPL]DWLRQ@f ZDV RQ WKH RUGHU RI b SHU VDPSOH 7KLV LV DOVR UHIOHFWHG LQ WKH HOHPHQWDO DQDO\VLV >b %U E\ ZHLJKW IRU FRPSOHWH DON\ODWLRQ FRPSDUHG WR WKH b %U IRXQG IRU 3371(W GURSf>@

PAGE 78

%URPRHWKDQH 7+) 57G 3371(W 3371(W )LJXUH 4XDWHPL]DWLRQ RI 3371(W WR IRUP 3371(W 3K\VLFDO 3URSHUWLHV RI 337 7\SH 3RO\PHUV )LJXUH VKRZV WKH 899LV DEVRUEDQFH DQG SKRWROXPLQHVFHQFH VSHFWUD IRU 3371(W>@ LQ 7+) DQG 3371(W>@ LQ +2 QRUPDOL]HG IRU FRQYHQLHQFHf ,W LV LQWHUHVWLQJ WR QRWH WKH GUDPDWLF VKLIW LQ DEVRUEDQFH PD[LPXP EHWZHHQ WKH QHXWUDO DQG FKDUJHG SRO\PHUV 3371(W>@ H[KLELWV D ;PD[ DW QP ZLWK D FRUUHVSRQGLQJ PRODU DEVRUSWLYLW\ RI DERXW / PROnnHPn ZKLOH 3371(W>@fV $PD[ LV EOXH VKLIWHG QP WR QP ZLWK D FRUUHVSRQGLQJ PRODU DEVRUSWLYLW\ RI DERXW / PROnnHPn 7KH EOXH VKLIW RI WKH Q WR r WUDQVLWLRQ IRU WKHVH SRO\PHUV PD\ EH GXH WR D VROYDWRFKURPLF HIIHFW )LQH WXQLQJ RI WKH ;PD[ FRXOG EH DFKLHYHG E\ FRQWUROOLQJ WKH H[WHQW RI TXDWHPL]DWLRQ DV LQFRPSOHWH TXDWHPL]DWLRQ OHDGV WR D ORZHU H[WHQW RI K\SVRFKURPLF VKLIW 6ROXWLRQ SKRWROXPLQHVFHQFH H[SHULPHQWV UHYHDOHG SHDN HPLVVLRQ ZDYHOHQJWKV RI QP DQG QP IRU 3371(W>@ LQ 7+) DQG 3371(W>@ LQ + UHVSHFWLYHO\

PAGE 79

7KH H[FLWDWLRQ ZDYHOHQJWK FRUUHVSRQGHG WR WKH ;PD[ RI HDFK SRO\PHUfV DEVRUEDQFH 7KH VSHFWUD GLVSOD\ WKH W\SLFDO FKDUDFWHULVWLFV RI FRQMXJDWHG SRO\PHUV LQ VROXWLRQ ZLWK D 6WRNHfV VKLIWHG HPLVVLRQ PD[LPXP DQG WDLOLQJ EURDGO\ WR KLJKHU ZDYHOHQJWKV 7DEOH VXPPDUL]HV WKH RSWLFDO SURSHUWLHV IRU ERWK WKH QHXWUDO DQG ZDWHU VROXEOH 337 SRO\PHUV :DYHOHQJWK QPf )LJXUH 1RUPDOL]HG 899LV DEVRUSWLRQ DQG VROXWLRQ SKRWROXPLQHVFHQFH IRU 337 1(W W\SH SRO\PHUV Df 3371(W>@ 899LV DEVRUSWLRQ LQ )(2 Ef 3371(W>@ 899LV DEVRUSWLRQ LQ 7+) Ff 3371(W>@ HPLVVLRQ LQ )(2 Gf 3371(W>@ HPLVVLRQ LQ 7+) ,W LV LQWHUHVWLQJ WR QRWH WKDW WKH WUHQG RI LQFUHDVHG DEVRUEDQFH DQG HPLVVLRQ LQWHQVLW\ ZKHQ PRYLQJ IURP QHXWUDO WR TXDWHPL]HG VSHFLHV IRU WKH 3331( V\VWHP ZDV

PAGE 80

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f )LOP &RORU (PLVVLRQ A‘PD[ QPf (PLVVLRQ &RORU 6ROXWLRQf 337 1(W>@ 5HG *UHHQ 337 1(W>@ 5HG *UHHQ 7KHUPDO GHDON\ODWLRQ RI WKH DPLQH VLWHV FDQ RFFXU LI WKH SRO\PHU LV H[SRVHG WR HOHYDWHG WHPSHUDWXUHV WKXV LQGLFDWLQJ D G\QDPLF HTXLOLEULXP DW WKH DPLQH VLWHV 7KLV GHn DON\ODWLRQ LV HYLGHQFHG LQ WKH 7*$ IRU 3371(W>@ VKRZQ LQ )LJXUH ZKHUH DQ LQLWLDO GHJUDGDWLRQ HYHQW VWDUWLQJ DW r& LV REVHUYHG IROORZHG FORVHO\ E\ ORVV RI WKH WULHWK\ODPLQH IUDJPHQW 7KH LQLWLDO ZHLJKW ORVV HYHQW LQ WKH GHJUDGDWLRQ RI 3371(W>@ RFFXUV DW r& FRUUHVSRQGLQJ WR WKH ORVV RI WKLV VDPH WULHWK\ODPLQH W\SH IUDJPHQW %RWK SRO\PHUV KDYH D ILQDO GHJUDGDWLRQ RFFXUULQJ RYHU r& DWWULEXWHG WR WKH EUHDNGRZQ RI WKH FRQMXJDWHG EDFNERQH DQG OLWWOH UHVLGXDO PDVV UHPDLQV

PAGE 81

&Rn f§L n n n Ua 7HPSHUDWXUH r&f )LJXUH 7*$ WKHUPRJUDPV IRU QHXWUDO DQG ZDWHU VROXEOH 3371(W XQGHU 1 Df 3371(W>@ Ef f§ 3371(W>@ &RQFOXVLRQV $ ZDWHU VROXEOH SRO\"SKHQ\OHQHFRWKLRSKHQHf 3371(W>@f KDV EHHQ V\QWKHVL]HG E\ D YDULHW\ RI PRGLILFDWLRQV RI 6WLOOH SRO\PHUL]DWLRQ WHFKQLTXHV 0D[LPXP PROHFXODU ZHLJKW ZDV DFKLHYHG LQ '0) XVLQJ 3G&O33Kf FDWDO\VW ZLWK VORZ DGGLWLRQ RI WKH ELVWULPHWK\OVWDQQ\Of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

PAGE 82

$GMXVWPHQW RI WKH QXPEHU RI 3371(W>@ OD\HUV GHSRVLWHG DQG WKLFNQHVV RI WKH OD\HUV GUDPDWLFDOO\ FKDQJHV DQG DOORZV ILQH WXQLQJ RI WKH UHIUDFWLYH LQGH[ RI WKH WUDQVSDUHQW fZLQGRZf FUHDWHG E\ WKH GHYLFH ,QYHVWLJDWLRQV RI WHVW UHDFWLRQV XVLQJ 6X]XNL FRXSOLQJ WHFKQLTXHV ZHUH VXFFHVVIXO XVLQJ D WKLRSKHQH GLERURQDWH HVWHU KRZHYHU WKH UHDJHQW ZDV WRR VXVFHSWLEOH WR K\GURO\VLV WR DOORZ WKH V\QWKHVLV RI KLJK PROHFXODU ZHLJKW SRO\PHUV DV HYLGHQFHG E\ D ORZHU DEVRUSWLRQ ZDYHOHQJWK PD[LPXP WKDQ WKH 6WLOOH SRO\PHUV 7KH WKLRSKHQH GLERURQDWH HVWHU LV D YLDEOH DOWHUQDWLYH WR PRUH KD]DUGRXV DQG WR[LF ELVWULDON\OVWDQQ\OfWKLRSKHQH UHDJHQWV IRU 3G FRXSOLQJ UHDFWLRQV WR GLVXEVWLWXWH WKLRSKHQH LQ WKH SRVLWLRQV

PAGE 83

&+$37(5 &$7,21,& 32/33(fV@ DUH D FODVV RI SRO\PHUV WKDW DUH FRPSRVHG RI DOWHUQDWLQJ SKHQ\O ULQJV DQG WULSOH ERQGV 7KH\ DUH VWUXFWXUDOO\ YHU\ VLPLODU WR WKH PXFK VWXGLHG SRO\PHU SRO\"SKHQ\OHQHYLQ\OHQHf >339@ LQ ZKLFK HOHFWUROXPLQHVFHQVH IURP D FRQMXJDWHG SRO\PHU ZDV ILUVW REVHUYHG 33(fV GLG QRW UHFHLYH WKH HDUO\ DWWHQWLRQ RI 339 EXW UHVHDUFK HIIRUWV KDYH LQFUHDVHG DV WKH OXPLQHVFHQW DQG FRQGXFWLQJ SURSHUWLHV RI 33( KDYH EHHQ VKRZQ WR EH XVHIXO IRU H[SORVLYH GHWHFWLRQ PROHFXODU ZLUHV WKDW EULGJH QDQRJDSV DQG SRODUL]HUV IRU OLTXLG FU\VWDOOLQH GLVSOD\V 7KH ILUVW V\QWKHVLV RI 33( ROLJRPHUV ZDV UHSRUWHG LQ DQG FRQVLVWHG RI KHDWLQJ FXSURXV DFHW\OLGH ZLWK GLLRGREHQ]HQH WR D GHJUHH RI SRO\PHUL]DWLRQ RI )LJXUH ODf 7KLV W\SH RI DSSURDFK DORQJ ZLWK GHK\GUREURPLQDWLRQ RI KDORJHQDWHG RU 339fV )LJXUH OEf DQG JHQHUDWLRQ RI 33( E\ HOHFWURFKHPLFDO UHGXFWLRQ RI KH[DKDOR S[\OHQH )LJXUH OFf ZDV XQVXFFHVVIXO LQ SUHSDULQJ ZHOOGHILQHG V\VWHPV ZLWKRXW GHIHFWV DQG VROXELOLW\ RI WKH UHVXOWLQJ VSHFLHV ZDV ORZ 33(fV KDYH DOVR EHHQ V\QWKHVL]HG E\ ULQJIRUPLQJ SRO\FRQGHQVDWLRQV VXFK DV WKH UHDFWLRQ RI DFHW\OHQGLFDUER[\OLF DPLGHV ZLWK K\GUD]LQH VXOIDWH LQ SRO\SKRVSKRULF DFLG 33$f IROORZHG E\ WKHUPDO F\FOL]DWLRQ RI WKH K\GUD]LGH JURXSV )LJXUH ,Gf DQG PRGLILFDWLRQV WR V\QWKHVL]H D ZLGH YDULHW\ RI ULJLG FRQMXJDWHG SRO\TXLQROLQHV )LJXUH OHf

PAGE 84

&Xf§f§f§&X 33( ROLJRPHUV %U &+&, r& 33( Ef &n? Faa FL &O ‘IFL &O &X HOHFWU 9 K 33( Ff 0 %X1&,ff 2 2 33$ \ f§ K1 1+ KVR +1 1+ Gf )LJXUH (DUO\ V\QWKHWLF PHWKRGRORJLHV WRZDUG SRO\"SKHQ\OHQHHWK\Q\OHQHffV >33(@ 3DOODGLXP f &RXSOLQJ 5HDFWLRQV 'XH WR WKH OLPLWDWLRQV RI WKH DERYH URXWHV SDOODGLXP FURVV FRXSOLQJ RI WHUPLQDO DON\QHV WR DURPDWLF EURPLGHV RU LRGLGHV LQ DPLQH VROYHQWV LV RIWHQ WKH SUHIHUUHG PHWKRGRORJ\ WR V\QWKHVL]H ZHOOGHILQHG DQG VROXEOH 33(fV 7KLV SURFHGXUH LV FDOOHG WKH

PAGE 85

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f (OHYDWHG WHPSHUDWXUHV QHFHVVDU\ IRU WKH EURPR UHDJHQWV FDQ OHDG WR FURVVOLQNLQJ DQG GHIHFW IRUPDWLRQ &KRLFH RI WKH DPLQH VROYHQW FDQ KDYH D GUDPDWLF HIIHFW RQ WKH UHDFWLRQ DQG LW KDV EHHQ IRXQG WKDW GLLVRSURS\ODPLQH LV DQ H[FHOOHQW FKRLFH IRU XVH ZLWK LRGRDUHQHV 33( SRO\PHUL]DWLRQV DUH FRQGXFWHG LQ FRQFHQWUDWHG VROXWLRQV DQG DPLQH VROYHQWV DORQH DUH QRW JRRG VROYHQWV IRU 33(fV WKHUHIRUH 7+) HWK\O HWKHU DQG WROXHQH DUH FRPPRQO\ XVHG FKRLFHV IRU FRVROYHQWV LQ WKH SRO\PHUL]DWLRQV 7KH DLU VWDEOH FRPPHUFLDOO\ DYDLODEOH 3G,,f FDWDO\VW 3G&K&33IA LV RIWHQ XVHG DV WKH VRXUFH RI 3Gf LQ WKH FRXSOLQJ UHDFWLRQ DQG PXVW EH UHGXFHG WR WKH DFWLYH 3Gf

PAGE 86

VSHFLHV DV RXWOLQHG LQ )LJXUH 7ZR PROHFXOHV RI D FXSUDWHG DON\QH WUDQVPHWDOODWH WKH 3G FDWDO\VW SUHFXUVRU DQG D V\PPHWULFDO EXWDGL\QH LV UHGXFWLYHO\ HOLPLQDWHG OHDYLQJ DQ DFWLYH 3Gf FDWDO\VW 3G&O33Kf LV XVHG LQ PRO b DPRXQWV DQG YDU\LQJ DPRXQWV RI &XO DUH XVHG DV DQ DON\Q\O DFWLYDWRU $FWLYDWLRQ RI WKH 3G,,f FDWDO\VW UHTXLUHV FRQVXPSWLRQ RI WKH DON\QH UHDJHQW ZKLFK PXVW EH DGMXVWHG DFFRUGLQJO\ LQ SRO\PHUL]DWLRQV WR HQVXUH D VWRLFKLRPHWULF EDODQFH ZLWK WKH KDORDURPDWLF FRPSRXQG $ SRVVLEOH DSSURDFK WR VROYLQJ WKH VWRLFKLRPHWULF EDODQFH SUREOHP LV WKH fSUHDFWLYDWLRQf RI WKH FDWDO\VW E\ DGGLWLRQ RI D PRQRIXQFWLRQDO DON\QH VXFK DV SKHQ\ODFHW\OHQHf WR WKH 3G,,f FDWDO\VW WKHUHE\ FRQYHUWLQJ LW WR 3Gf 7KH FDWDO\VW VROXWLRQ FRXOG WKHQ EH DGGHG WR WKH SRO\PHUL]DWLRQ UHDJHQWV DQG WKH GL\QH E\SURGXFW RI WKH FDWDO\VW DFWLYDWLRQ ZRXOG QRW LQWHUIHUH ZLWK WKH VWRLFKLRPHWULF EDODQFH 5HGXFWLYH (OLPLQDWLRQ 3URGXFW )LJXUH $FWLYDWLRQ RI 3G,,f FRPSRXQG WR DFWLYH 3Gf FDWDO\VW

PAGE 87

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f RI VLPLODU 33(fV ZDV DFKLHYHG E\ 0RURQL HW DO ZLWK GHJUHHV RI SRO\PHUL]DWLRQ RI DSSUR[LPDWHO\ 7KHVH ZRUNHUV GLG QRW WDNH LQWR DFFRXQW WKH DFWLYDWLRQ RI WKH SDOODGLXP FDWDO\VW WKXV ORZHULQJ PROHFXODU ZHLJKWV DQG LQWURGXFLQJ GL\QH GHIHFWV LQ WKH EDFNERQH 25 25 )LJXUH 6\QWKHVLV RI GLDONR[\ SRO\"SKHQ\OHQHHWK\Q\OHQHffV YLD WKH 6RQRJDVKLUD UHDFWLRQ 5HGXFWLRQ RI UHDFWLRQ WHPSHUDWXUHV WR ORZHU WKDQ r& E\ :ULJKWRQ HW DO LQ WKH FRXSOLQJ RI GLLRGROGLDONR[\EHQ]HQHV WR GLHWK\Q\OOGLDONR[\EHQ]HQHV LQ D

PAGE 88

GLLVRSURS\ODPLQHWROXHQH PL[WXUH XQGHU 3G&KL33KA9&X, FDWDO\VLV OHG WR SRO\PHUV ZLWKRXW FURVVOLQNLQJ DQG GHJUHHV RI SRO\PHUL]DWLRQ RI XS WR 7KH VDPH JURXS SUHSDUHG LQWHUHVWLQJ GLDONR[\VXEVWLWXWHG FRSRO\PHUV ZLWK GLPHWK\ODPLQRfSURS\O DQG FDUER[\KHSW\O JURXSV :HGHU HW DO XWLOL]HG WKH EUDQFKHG VROXELOL]LQJ HWK\OKH[\OR[\ DQG OLQHDU RFW\OR[\ JURXSV WR SUHSDUH D SRO\PHU ZLWK D UHSRUWHG GHJUHH RI SRO\PHUL]DWLRQ RI ZKLFK ZHUH VXPPDULO\ UHIOHFWHG LQ WKH VLPLODU ZRUN RI 6ZDJHU DQG FRZRUNHUV ZKR OLPLWHG WKH PROHFXODU ZHLJKW E\ WKH XVH RI DQ LPEDODQFHG UHDFWLRQ VWRLFKLRPHWU\ WR HQVXUH GHILQHG LRGLQH HQGJURXSV 2WKHU FODVVHV RI 33(fV KDYH EHHQ FUHDWHG YLD WKH 6RQRJDVKLUD UHDFWLRQ WKDW PL[ GLDONR[\VXEVWLWXWHG GLLRGLGHV ZLWK GLIIHUHQW DURPDWLF GL\QHV ([DPSOHV LQFOXGH :HVWfV XVH RI GLHWK\Q\OEHQ]HQH )LJXUH Df DQG 6ZDJHUfV XVH RI DO QR GLHWK\Q\OSHQWLSW\FHQH PRQRPHU WR SURYLGH EXON\ FKDLQ VSDFLQJ VLGHJURXSV )LJXUH Ef RU D ELVDPLGH FRPSRXQG EHWWHU ILOP IRUPLQJ SURSHUWLHV )LJXUH Ff $U\O DQG DON\OVXEVWLWXWHG 33(fV ZKLFK UHVHPEOH D fWUXHf XQVXEVWLWXWHG 33( WKH PRVW ZHUH ILUVW UHSRUWHG LQ E\ %XQ] DQG 0XOOHQ )LJXUH Gf $ FRPSOHWH FRYHUDJH RI DOO 33( W\SH SRO\PHUV V\QWKHVL]HG E\ 3Gf FRXSOLQJ PHWKRGRORJLHV ZRXOG EH LPSRVVLEOH LQ WKLV GLVVHUWDWLRQ KRZHYHU WZR H[FHOOHQW UHYLHZV E\ *LHVD DQG %XQ] RQ WKH VXEMHFW PDWWHU DUH DYDLODEOH IRU UHIHUHQFH ([WHQVLYH ZRUN KDV DOVR EHHQ DFFRPSOLVKHG LQ WKH ILHOG RI PHWDO WR OLJDQG FKDUJH WUDQVIHU EHWZHHQ 33(fV DQG FRRUGLQDWHG PHWDOOLF VSHFLHV 7KH XWLOLW\ RI WKH 6RQRJDVKLUD UHDFWLRQ IRU V\QWKHVL]LQJ ZHOOGHILQHG 33(fV DORQJ ZLWK LWV WROHUDQFH IRU IXQFWLRQDO JURXSV PDNHV LW DSSOLFDEOH IRU LQFRUSRUDWLRQ RI GLDONR[\DPLQHSKHQ\OHQH XQLWV LQWR D 33( EDFNERQH VWUXFWXUH 7KHVH XQLWV FDQ EH SURWRQDWHG ZLWK DFLGLF WUHDWPHQW RU TXDWHPL]HG ZLWK HWK\OEURPLGH WR SURYLGH DQ

PAGE 89

LQWHUHVWLQJ QHZ FODVV RI SRO\HOHFWURO\WH ,Q JHQHUDO VXFK SRO\PHUV VKRXOG EH \HOORZ LQ FRORU DQG HPLW LQ WKH JUHHQ UHJLRQ RI WKH YLVLEOH FRORU VSHFWUXP 'XH WR WKH H[WHQVLYH ULJLGURG FKDUDFWHU RI 33(fV VSHFLDO FDUH ZLOO KDYH WR EH WDNHQ ZLWK WKH UHVXOWLQJ PDWHULDOV WR GHWHUPLQH WKH HIIHFW GLIIHUHQW VLGH FKDLQV RQ WKH VHFRQG SKHQ\OHQH ULQJ LQ WKH UHSHDW XQLW ZLOO KDYH RQ WKH VROXELOLW\ RI WKH LQLWLDO QHXWUDO SRO\PHU DQG VXEVHTXHQWO\ WKH HIIHFW RI EXON\ RUJDQLF JURXSV RQ WKH SURSHUWLHV RI WKH SRVWSRO\PHUL]DWLRQ TXDWHPL]HG SRO\PHU ,I VXFFHVVIXO WKLV VHW RI 33( SRO\PHUV PD\ SURYLGH SRO\PHUV WKDW HPLW LQ D VLPLODU ZDYHOHQJWK UDQJH DV WKH SRO\SSKHQ\OHQHFRWKLRSKHQHVf >337fV@ GLVFXVVHG LQ &KDSWHU DQG DUH PRUH HIILFLHQW HPLWWHUV ZKLFK DUH FDSDEOH RI EHLQJ FDVW DV IUHH VWDQGLQJ WKLQ ILOPV AA &+L )LJXUH 5HSUHVHQWDWLYH VWUXFWXUHV RI V\QWKHWLF PRGLILFDWLRQV WR SRO\S SKHQ\OHQHHWK\Q\OHQHffV

PAGE 90

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r& IRU KRXUV FRROHG SRXUHG LQWR LFH ZDWHU DQG H[WUDFWHG ZLWK KH[DQHV 7KH RUJDQLF OD\HU ZDV VXEVHTXHQWO\ ZDVKHG ZLWK 0 1D2+ ZDWHU EULQH &RPSRXQG b
PAGE 91

S&J+A +L& RU 2&J+LJ +& .,2 n $F2+ + +6 r& K 2&J+A +L& RU &RPSRXQG b @ ZHUH LVRODWHG YLD ILOWUDWLRQ RI WKH UHDFWLRQ WR UHPRYH DPLQH VDOWV DQG SDVVHG WKURXJK D ILOWHU SOXJ RI VLOLFD JHO XVLQJ WROXHQH DV HOXHQW $IWHU UHPRYDO RI WKH VROYHQW FUXGH UHG VROLGV ZHUH REWDLQHG DQG UHFU\VWDOOL]HG WZLFH IURP HWKDQRO WR \LHOG ZKLWH FU\VWDOV 7KH ELVWULPHWK\OVLO\OfHWK\Q\Of FRPSRXQGV ZHUH WUHDWHG ZLWK HLWKHU WHWUDEXW\ODPPRQLXP IOXRULGH RU DTXHRXV .2+ LQ 7+) WR UHPRYH WKH 706 JURXSV 7KH GLHWK\Q\O FRPSRXQGV f VKRZQ LQ )LJXUH ZHUH UHFRYHUHG LQ RYHUDOO WR SHUFHQW \LHOGV EDVHG RQ

PAGE 92

WKH DSSURSULDWH VWDUWLQJ GLLRGLGH FRPSRXQG DV OLJKW \HOORZ RU ZKLWH FU\VWDOV (OHPHQWDO DQDO\VLV UHVXOWV IRU FRPSRXQGV DUH OLVWHG LQ 7DEOH S&J+L 2&+ 706f§f§ ?f§(A706 + +L& HT +L& RU + 6L ? 3G&,33Kf &XO (W1 $ 2&+L S +L& RU + 7%$) RU DT .2+ 7+) + 706f§f§ 9f§Af§706 + + &RPSRXQG b 99GLHWK\ODPLQR@O R[DSURS\OfOGLLRGREHQ]HQH ',1(Wf ZDV XVHG LQ FRQMXQFWLRQ ZLWK WKH DERYH GL HWK\Q\O FRPSRXQGV IRU 6RQRJDVKLUD SRO\PHUL]DWLRQV WR SURYLGH D IXQFWLRQDO DPLQH VLWH WR EH TXDWHPL]HG DIWHU SRO\PHUL]DWLRQ VHH &KDSWHU f 6\QWKHVLV RI ELV>$IL9 GLHWK\ODPLQR@OR[DSURS\OfOGLHWK\Q\OEHQ]HQH SURGXFHG E\ 3Gf FRXSOLQJ RI ',1(W ZLWK WULPHWK\OVLO\ODFHW\OHQH DQG WUHDWPHQW ZLWK EDVH ZDV DWWHPSWHG LQ RUGHU WR KDYH D FRPSDQLRQ UHDJHQW WR ',1(W ZKLFK XSRQ 6RQRJDVKLUD SRO\PHUL]DWLRQ ZLWK ',1(W ZRXOG SURGXFH D 33( ZLWK HYHU\ SKHQ\OHQH ULQJ SRVVHVVLQJ DONR[\DPLQH VLGH FKDLQV

PAGE 93

3XULILFDWLRQ RI WKH ELV>9\9GLHWK\ODPLQR@OR[DSURS\OfOGLHWK\Q\OEHQ]HQH WR D OHYHO VDWLVIDFWRU\ IRU XVH LQ VWHS JURZWK SRO\PHUL]DWLRQV ZDV KLQGHUHG JUHDWO\ E\ WKH 7DEOH (OHPHQWDO DQDO\VLV UHVXOWV IRU 33( PRQRPHUV DQG SRO\PHUV 6SHFLHV b& b+ b1 b? RU %U $QDO &DOHG IRU &RPSRXQG 7KHR &+2 ([S &RPSRXQG 7KHR &+2 ([S &RPSRXQG 7KHR &LR+ ([S 33(1(+ 7KHR &+12, >@ ([S 33(1( 7KHR & +12, 2& >@ ([S 33(1(WV 2&+LJKf 7KHR ,f &+12, >@ ([S ,f 33(1(W] 7KHR ,f &+12, 2&f >@ ([S ,f 33(1(W 2&f 7KHR %Uf &+12 f &+% &+12 f &+%U >@ ([S %Uf H[WUHPHO\ SRODU DPLQH VLWHV ZKLFK SUHYHQWHG FROXPQ FKURPDWRJUDSK\ 2WKHU PHDQV RI SXULILFDWLRQ ZHUH XQVXFFHVVIXO LQ WKDW GLVWLOODWLRQ XQGHU UHGXFHG SUHVVXUH UHVXOWHG LQ WKH

PAGE 94

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fOGLLRGREHQ]HQH ZKLFK SURYLGHV DQ RSWLRQDO PRQRPHU WR ',1(W ,W VKRXOG EH QRWHG WKDW WKLV PRQRPHU GRHV QRW KDYH DONR[\ EXW UDWKHU DON\O VLGH FKDLQV DQG XSRQ LQFRUSRUDWLRQ LQWR D SRO\PHU EDFNERQH ZRXOG UDLVH WKH HQHUJ\ RI WKH Q WR Qr WUDQVLWLRQ FRPSDUHG WR DONR[\ FRQWDLQLQJ 33(f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

PAGE 95

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f FDW )LJXUH 6\QWKHVLV RI ELVEURPRKH[\Of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

PAGE 96

LQ b \LHOG DV D ZKLWH FU\VWDOOLQH VROLG DIWHU UHFU\VWDOOL]DWLRQ IURP PHWKDQRO EDVHG RQ WKH DPRXQW RI FRPSRXQG XVHG RYHUDOO b \LHOG EDVHG RQ VWDUWLQJ FRPSRXQG f 5HKDKQ HW DO GHPRQVWUDWHG WKH WHFKQLTXH RI fSURWHFWLQJf WKH EURPLQH JURXSV E\ HWKHULILFDWLRQ ZLWK SKHQRO DQG UHDFWLQJ WKHLU ELVSKHQ\R[\KH[\OfO GLEURPREHQ]HQH ZLWK YDULRXV SKHQ\OHQH ERURQLF UHDJHQWV WR FUHDWH SRO\SSKHQ\OHQHffV 7KH SKHQR[\ HQG JURXSV FRXOG EH FRQYHUWHG SRVWSRO\PHUL]DWLRQ LQWR LRGR IXQFWLRQDOLWLHV E\ WUHDWPHQW ZLWK WQPHWK\OLRGRVLODQH IROORZHG E\ H[SRVXUH WR WULHWK\ODPLQH WR SURGXFH FKDUJHG FDWLRQLF DPLQH VLWHV DORQJ WKH EDFNERQH RI WKH SRO\PHU VHH )LJXUH f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fV VHH )LJXUH ZKLFK FDQ EH WUHDWHG LQ WKH VDPH PDQQHU DV WKH 333fV LQ )LJXUH WR DFKLHYH FKDUJHG DPLQH VLWHV DORQJ WKH EDFNERQH $V WKH SXUSRVH RI WKLV ERG\ RI ZRUN LV WR IRFXV RQ GLDONR[\ VXEVWLWXWHG 33(fV SRO\PHUL]DWLRQV XWLOL]LQJ ELV SKHQR[\KH[\OfOGLLRGREHQ]HQH >@ ZHUH QRW FRQGXFWHG +RZHYHU WKH VRPHZKDW GLIILFXOW PRQRPHU V\QWKHVLV KDV EHHQ ILQH WXQHG WR DOORZ WKH SXUVXLW RI WKHVH W\SH RI 33( SRO\PHUV E\ IXWXUH ZRUNHUV

PAGE 97

L L PLQ )LJXUH *DV FKURPDWRJUDSK\ DQDO\VLV RI SXULILFDWLRQ RI EURPRKH[\OPHWK\OHWKHU f E\ YDFXXP GLVWLOODWLRQ XVLQJ Df VLPSOH YLJUHX[ FROXPQ DQG Ef VSLQQLQJ EDQG FROXPQ

PAGE 98

&+23K 6X]XNL 3RO\PHUL]DWRQ 7ULPHWK\OLRGRVLODQH 5 FKL (W1 5 &+1(W ??B9a \ Y-Q $&1 \ YQ 5 &+, 5 &+1(W )LJXUH 5HKDKQfV URXWH WR FDWLRQLF 333fV R A )LJXUH :LOOLDPVRQ HWKHULILFDWLRQ WR fSURWHFWf EURPR HQGJURXSV &+23K 7ULPHWK\OLRGRVLODQH Q &+23K )LJXUH (QYLVLRQHG DSSOLFDWLRQ RI 5HKDKQfV VWUDWHJ\ WR 33(fV

PAGE 99

1HXWUDO 3RO\PHU 6\QWKHVHV 7KH JHQHUDO 6RQDJDVKLUD SRO\PHUL]DWLRQ LV RXWOLQHG LQ )LJXUH ',1(W GL HWK\Q\O FRPSRXQG &XO FRFDWDO\VW DQG 3G FDWDO\VW RI FKRLFH ZHUH VWLUUHG LQ D VROXWLRQ RI WROXHQH DQG DPLQH WULHWK\ODPLQH RU GLLVRSURS\ODPLQHf ZLWK KHDWLQJ WR r& 7HPSHUDWXUHV DERYH r& DUH NQRZQ WR SURPRWH FURVVOLQNLQJ LQ WKH 33( FKDLQV DORQJ ZLWK XQGHVLUHG GL\QH GHIHFWV DQG ZHUH WKHUHIRUH DYRLGHG :KHQ 3G,,f FDWDO\VWV DUH HPSOR\HG WKH DPRXQW RI GLHWK\Q\O FRPSRXQG VKRXOG EH DGMXVWHG WR DFFRXQW IRU UHGXFWLRQ RI WKH FDWDO\VW WR 3Gf DV VKRZQ LQ )LJXUH 3Gf FDWDO\VWV VXFK DV 3G33Kf DUH HIIHFWLYH IRU WKH FRXSOLQJ DQG GR QRW QHHG WR EH UHGXFHG EHIRUH EHJLQQLQJ WKH FDWDO\WLF F\FOH EXW FDUHIXO H[FOXVLRQ RI 2 IURP WKH UHDFWLRQ PXVW EH FRQGXFWHG )RU WKH SRO\PHUL]DWLRQV LQ WKLV VWXG\ GLLVRSURS\ODPLQH DQG 3G33Kf ZHUH XVHG LQ DOO FRXSOLQJV ',1(W 1 5 3RO\PHU 5 0RQRIXQFWLRQDO (QGFDSSLQJ $JHQW IRU 33(1(W2&f 33(1(W+>@ + 33(1(W2&>@ 2&+ 33(1(W2&KLJKf >@ 2&+ 33(1(W2&f >@ 2&+ )LJXUH *HQHUDO V\QWKHVLV IRU DONR[\DPLQH FRQWDLQLQJ 33(fV

PAGE 100

,QLWLDO V\QWKHWLF DWWHPSWV DW SURGXFLQJ XVHIXO 33(fV ZHUH SHUIRUPHG ZLWK WKH FRXSOLQJ RI ',1(W WR GLHWK\Q\OEHQ]HQH XVLQJ WROXHQH GLLVRSURS\ODPLQH VROYHQW V\VWHP 0 LQ ',1(Wf DQG PROb 3G33ILf &XO FDWDO\VWV 33(1(W+>@f $ VOLJKW H[FHVV RI GLHWK\Q\O FRPSRXQG LV XVHG a PRO bf HYHQ ZLWK DQ LQLWLDO 3Gf FDWDO\VW WR DFFRXQW IRU XQDYRLGDEOH VLGH UHDFWLRQV RI WKH FRPSRXQG $IWHU D UHDFWLRQ WLPH RI KRXUV D QRWLFHDEOH DPRXQW RI PDWHULDO ZDV SUHFLSLWDWLQJ IURP WKH UHDFWLRQ IODVN $IWHU FRROLQJ WKH UHDFWLRQ DIWHU KRXUV WKH PL[WXUH ZDV SRXUHG LQWR FROG HWKDQRO DQG D \HOORZ VROLG UHFRYHUHG LQ QHDUO\ TXDQWLWDWLYH \LHOG 7KLV \HOORZ PDWHULDO ZDV LQVROXEOH LQ KRW FKORURIRUP 7+) RU WROXHQH 7KLV UHVXOW ZDV QRW XQH[SHFWHG DV 33(f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f+ 105 RU *3&f ZDV H[FOXGHG E\ WKH LQVROXELOLW\ RI WKH PDWHULDO (OHPHQWDO DQDO\VLV RI WKH PDWHULDO ZDV FRQVLVWHQW ZLWK WKH SURSRVHG UHSHDW XQLW VWUXFWXUH VHH 7DEOH f /RQJHU DONR[\ JURXSV ZHUH WKHQ XVHG RQ WKH GLHWK\Q\O UHDJHQW LQ KRSHV RI DGGLQJ VROXELOLW\ LQ RUJDQLF VROYHQWV WR WKH QHXWUDO 33(fV 3RO\PHUL]DWLRQ RI FRPSRXQG OGLHWK\Q\OELVKH[\OR[\fEHQ]HQH ZLWK ',1(W XQGHU WKH VDPH FRQGLWLRQV DV OLVWHG DERYH IRU 33(1(W+>@ ZDV XQGHUWDNHQ 33(1(W2&>@f 2YHU WKH FRDUVH RI KRXUV WKH JURZLQJ SRO\PHU UHPDLQHG LQ VROXWLRQ ZLWK QR HYLGHQFH RI D

PAGE 101

SRO\PHU FRDWLQJ RQ WKH UHDFWLRQ YHVVHO :KHQ H[FLWHG E\ D 89 ODPS DQ LQWHQVH \HOORZ JUHHQ HPLVVLRQ ZDV REVHUYHG 8SRQ FRROLQJ H[FHVV VROYHQW ZDV UHPRYHG DQG WKH UHPDLQLQJ VROXWLRQ ZDV SUHFLSLWDWHG LQWR 0H2+ 4XDQWLWDWLYH \LHOG RI D \HOORZRUDQJH PDWHULDO ZDV UHFRYHUHG DQG H[WUDFWHG VXFFHVVLYHO\ ZLWK 0H2+ DFHWRQH DQG &+&, YLD 6R[KOHW H[WUDFWLRQ 2QO\ b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f>@f DQG WKH RWKHU SRO\PHUL]DWLRQ ZDV FRQGXFWHG ZLWK WKH DGGLWLRQ RI D VPDOO DPRXQW RI LRGREHQ]HQH WR OLPLW FKDLQ OHQJWK WKHRUHWLFDOO\ FDOFXODWHG WR JLYH D GHJUHH RI SRO\PHUL]DWLRQ RI ULQJVf XVLQJ VLPSOH VWHSJURZWK SRO\PHUL]DWLRQ HTXDWLRQVf WR V\QWKHVL]H 33(1(W!2&f>@ 7KH DGGLWLRQ RI WKH HQGFDSSLQJ UHDJHQW VKRXOG OLPLW FKDLQ OHQJWK WR LPSURYH VROXELOLW\ DQG JLYH GHILQLWLYH n+ 105 VLJQDOV IRU GHWHUPLQDWLRQ RI QXPEHU DYHUDJH PROHFXODU ZHLJKWV 'XULQJ WKH FRDUVH RI SRO\PHUL]DWLRQ 33(1(W2&+LJKf>@ IRUPHG D JHOOLNH VXVSHQVLRQ LQGLFDWLQJ D

PAGE 102

YHU\ KLJK H[WHQW RI SRO\PHUL]DWLRQ ZKLOH 33(1(W2&f>@ UHPDLQHG VROXEOH 7KH fJHOf ZDV IXOO\ GLVVROYHG E\ WKH DGGLWLRQ RI DQ H[FHVV RI FKORURIRUP %RWK UHDFWLRQV ZHUH SUHFLSLWDWHG LQWR DFHWRQH DIWHU KRXUV DQG WKH FROOHFWHG SRO\PHUV ZHUH ZDVKHG WKRURXJKO\ ZLWK KRW HWKDQRO DFHWRQH DQG DFHWRQLWULOH 33(1(W2&+LJKf>@ EHFDPH LQVROXEOH XSRQ FRPSOHWH GU\LQJ ZLWK OLJKW KHDWLQJ XQGHU YDFXXP (OHPHQWDO DQDO\VLV RI 33(1(W2&+LJKf LQGLFDWHG b LRGLQH E\ ZHLJKW SUHVHQW LQ WKH VDPSOH ZKLFK ZLWK WKH DVVXPSWLRQ WKDW WKHUH LV RQH LRGLQH PROHFXOH SHU FKDLQ LQGLFDWHV D GHJUHH RI SRO\PHUL]DWLRQ RI ULQJVf $ VPDOO DPRXQW RI WKH GULHG 33(1(W2&f>@ ZRXOG GLVVROYH LQ UHIOX[LQJ FKORURIRUP DQG D FUXGH f+ 105 ZDV DFTXLUHG IRU WKH VROXEOH SRUWLRQ 7KH VSHFWUXP ZDV FRQVLVWHQW ZLWK WKH SURSRVHG SRO\PHU VWUXFWXUH EXW HQGJURXS DQDO\VLV ZDV QRW GHILQLWLYH GXH WR WKH ORZ FRQFHQWUDWLRQ RI WKH 105 VDPSOH DQG WKH LQKHUHQW IUDFWLRQDWLRQ RI WKH PDWHULDO 7KH DELOLW\ RI WKH FKDLQV WR SDFN LQ ZHOOGULHG VROLG IRUP SUHYHQWV UHVROYDWLRQ RI WKH SRO\PHU FKDLQV DQG UHQGHUV WKH PDWHULDOV XQXVDEOH $IWHU WKH LQLWLDO ZRUN RQ WKH SRO\PHUV DERYH LW ZDV GHFLGHG WR UHSHDW WKH 33(1(W2&f>@ SRO\PHUL]DWLRQ DQG SUHYHQW WKH FRPSOHWH GU\LQJ RI WKH PDWHULDO :RUN ZLWK 33(1(W2&f>@ ZDV FKRVHQ RYHU 33(1(W2&+LJKf>@ WR HQVXUH WKH JUHDWHVW FKDQFH RI PDLQWDLQLQJ VROXELOLW\ :LWK D GHJUHH RI SRO\PHUL]DWLRQ RI 33(1(W2&f>@ ZLOO KDYH DWWDLQHG LWV PD[LPXP RSWLFDO DEVRUSWLRQ DQG HPLVVLRQ DQG LI VROXELOLW\ FDQ EH PDLQWDLQHG ZLOO SURYLGH D XVHIXO SRO\PHU ,W ZDV GHFLGHG QRW WR H[WHQG WKH OHQJWK RI WKH DONR[\ FKDLQ WR KHOS SUHYHQW FKDLQ SDFNLQJ DV VXFK DQ LQFUHDVH LQ WKH RUJDQLF QDWXUH RI WKH SRO\PHU ZRXOG EH GHWULPHQWDO WR WKH GHVLUHG ZDWHU VROXELOLW\ RI WKH FDWLRQLF GHULYDWLYHV WR EH SURGXFHG DIWHU SRO\PHUL]DWLRQ 7KH VHFRQG V\QWKHVLV RI 33(1(W2&f>@

PAGE 103

SURYLGHG D SRO\PHU WKDW PDLQWDLQHG VROXELOLW\ WR D UHDVRQDEOH OHYHO LQ FKORURIRUP a PJP/f DIWHU GU\LQJ RYHUQLJKW LQ D VWHDG\ VWUHDP RI DLU 7KH SRO\PHU ZDV EULJKW \HOORZ LQ FRORU LQGLFDWLQJ OLWWOH FURVVOLQNLQJ RU GL\QH GHIHFWV KDG RFFXUUHG DQG ZDV UHFRYHUHG LQ KLJK \LHOG bf 'HWHUPLQDWLRQ RI WKH PROHFXODU ZHLJKW RI WKH ULJLG 33(1(W2&f>@ YLD VWDQGDUG JHO SHUPHDWLRQ FKURPDWRJUDSK\ *3&f SURYHG LQFRQFOXVLYH $OWKRXJK VXIILFLHQWO\ VROXEOH LQ FKORURIRUP WR SHUIRUP WKH DQDO\VLV SHDNV GHWHFWHG E\ 89 DEVRUSWLRQ DSSHDUHG RQO\ DW WKH HQG RI WKH FROXPQ YROXPH 7KH 33( SRO\PHU LQWHUDFWHG ZLWK DQG DGVRUEHG WR WKH FROXPQ SDFNLQJ PDWHULDO LQ VXFK D ZD\ DV WR SUHYHQW VHSDUDWLRQ E\ VL]H 7KLV LV QRW DQ XQFRPPRQ SKHQRPHQRQ HVSHFLDOO\ ZLWK SRODU SRO\PHUV ZKLFK FDQ SRVVLEO\ ELQG WR WKH FROXPQ PDWHULDO 7KH ULJLG QDWXUH RI WKH SRO\PHUV H[FOXGLQJ FROXPQ fVWLFNLQJf HIIHFWV QRUPDOO\ FDXVH D GHFUHDVH LQ WKH UHWHQWLRQ WLPH RI WKH VDPSOH ZKHQ FRPSDUHG WR SRO\VW\UHQH VWDQGDUGV RI WKH DSSUR[LPDWH VDPH PROHFXODU ZHLJKW IXUWKHU FRPSOLFDWLQJ PROHFXODU ZHLJKW GHWHUPLQDWLRQ E\ WKLV PHWKRG f+ 105 89 DEVRUEDQFH DQG ILOP FDVWLQJ ZHUH XVHG WR VXEVWDQWLDWH WKDW WKH PDWHULDO ZDV SRO\PHULF )UHH VWDQGLQJ RUDQJH ILOPV RI 33(1(W2&f>@ FRXOG EH FDVW IURP FKORURIRUP VROXWLRQV RQWR JODVV RU 7HIORQp VXEVWUDWHV )LJXUH VKRZV ERWK WKH nLG DQG OM& 105 IRU 33(1(W2&f>@ LQ &'&, ZKLFK JDYH H[SHFWHG VKLIW YDOXHV ZLWK WKH SURWRQ SHDNV DSSHDULQJ DV EURDG PXOWLSOHWV ZLWK SRRU VSOLWWLQJ )LJXUH VKRZV DQ H[SDQVLRQ RI WKH DURPDWLF UHJLRQ DORQJ ZLWK LQWHJUDO YDOXHV IRU WKH SHDNV LQ RUGHU WR FDOFXODWH DQ DSSUR[LPDWH GHJUHH RI SRO\PHUL]DWLRQ IRU 33(1(W2&f>@

PAGE 104

N 7 U L f L Uf§U 6 = & 105 3HDNV SSP )LJXUH n+ DQG & 105 RI 33(1(W2&f>@ LQ &'&

PAGE 105

%DVHG RQ WKH HQGFDSSHG SRO\PHU UHSHDW XQLW VWUXFWXUH VKRZQ LQ )LJXUH WKH QXPEHU RI UHSHDW XQLWV Q FDQ EH FDOFXODWHG IURP f+ 105 LQWHJUDWLRQ YDOXHV XVLQJ WKH IRUPXOD ] F D f ZKHUH Q ULQJVf RU VXEVHTXHQWO\ D 0Q JPRO ,W VKRXOG EH QRWHG WKDW WKLV QXPEHU LV DQ DSSUR[LPDWLRQ DQG VHYHUDO IDFWRUV VKRXOG EH FRQVLGHUHG ZKHQ XVLQJ WKLV DSSUR[LPDWLRQ VXFK DV SRVVLEOH HUURUV LQ WKH 105 LQWHJUDWLRQ YDOXHV DQG WKH SUHVHQFH RI LRGLQH bf LQ WKH VDPSOH ZKLFK LQGLFDWHV QRQHQGFDSSHG FKDLQ HQGV $VVXPLQJ D OLEHUDO HVWLPDWLRQ RI WKHVH HUURUV LW LV VDIH WR DVVXPH WKDW PLQLPDOO\ D '3 0Q JPRO ULQJVf KDV EHHQ DFKLHYHG )LJXUH ([SDQVLRQ RI WKH DURPDWLF UHJLRQ RI WKH f+ 105 RI 33( 1(W2&f>@ LQ &'&

PAGE 106

3RO\PHU 4XDWHPL]DWLRQ )LJXUH RXWOLQHV WZR URXWHV WR V\QWKHVL]LQJ FDWLRQLF SRO\HOHFWURO\WHV IURP 33(1(W2&f>@ 'LUHFW WUHDWPHQW RI WKH QHXWUDO SRO\PHU LQ (W2+ ZLWK 0 +& WR ORZHU S+ DQG SURWRQDWH WKH DPLQH VLWHV ZDV D VXFFHVVIXO PHWKRGRORJ\ WR FUHDWH D SRO\HOHFWURO\H 33(1(W+2&f>@ WKDW ZDV VROXEOH LQ WKH ORZHUHG S+ HWKDQRO DQG GLVSOD\HG LQWHUHVWLQJ SK\VLFDO SURSHUWLHV GLIIHUHQW IURP WKH QHXWUDO YHUVLRQ WR EH GLVFXVVHG LQ 3K\VLFDO 3URSHUWLHV VHFWLRQf 8QIRUWXQDWHO\ WKH 33(1(W+2&f>@ ZDV QRW VROXEOH LQ ORZHUHG S+ ZDWHU DORQH EXW UHTXLUHG WKH DGGLWLRQ RI HWKDQRO RU SURSDQRO WR GLVVROYH 6ROXWLRQV RI WKH QHXWUDO SRO\PHU LQ ORZHUHG S+ HWKDQRO ZHUH FDVW RQWR 7HIORQp DQG FRXOG EH UHPRYHG DV IUHH VWDQGLQJ WKLQ ILOPV 7KH VROXWLRQV DOVR KDYH WKH FDSDELOLW\ WR EH GLUHFWO\ XVHG LQ HOHFWURVWDWLF GHSRVLWLRQ H[SHULPHQWV DQG DYRLG WKH DGGHG V\QWKHWLF VWHS RI TXDWHPL]DWLRQ ZLWK EURPRHWKDQH DQG LWV GLIILFXOWLHV WR EH GHVFULEHG EHORZ )LJXUH &RQYHUVLRQ RI 33(1(W2&f>@ WR FDWLRQLF SRO\HOHFWURO\WHV

PAGE 107

7UHDWPHQW RI 33(1(W2&f>@ LQ D r& FKORURIRUPDFHWRQLWULOH VROXWLRQ ZLWK EURPRHWKDQH WR V\QWKHVL]H 33(1(W2&f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b EURPLQH FRQWHQW E\ ZHLJKW LQGLFDWLQJ D b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f>@ ZKLFK ZLOO EH GLVFXVVHG LQ GHWDLO LQ WKH 3K\VLFDO 3URSHUWLHV VHFWLRQ %DVHG RQ WKHVH REVHUYDWLRQV DQG UHVXOWV LW ZDV GHWHUPLQHG WKDW 33( 1(W+2&f>@ FRXOG EH XVHG DV DQ HIIHFWLYH DOWHUQDWLYH WR D EURPRHWKDQH TXDWHPL]HG SRO\HOHFWURO\WH DQG WKHUHIRUH WKH SURSHUWLHV RI 33(1(W+2&f>@ ZHUH LQYHVWLJDWHG PRUH IXOO\ WKDQ WKRVH RI WKH 33(1(W2&f>@ PDWHULDO 3K\VLFDO 3URSHUWLHV RI 33( 7\SH 3RO\PHUV )LJXUH VKRZV WKH 899LV DEVRUEDQFH DQG SKRWROXPLQHVFHQFH VSHFWUD IRU 33(1(W2&f>@ LQ &+& DQG 33(1(W+2&f>@ LQ ORZ S+ (W2+

PAGE 108

QRUPDOL]HG IRU FRQYHQLHQFHf ,W LV LQWHUHVWLQJ WR QRWH WKH GUDPDWLF VKLIW LQ DEVRUEDQFH PD[LPXP EHWZHHQ WKH QHXWUDO DQG FKDUJHG SRO\PHUV 33(1(W2&f>@ H[KLELWV D $PD[ DW QP ZLWK D FRUUHVSRQGLQJ PRODU DEVRUSWLYH RI DERXW / PROnFPn ZKLOH 33(1(W+2&f>@fV $PD[ LV EOXH VKLIWHG QP WR QP ZLWK D FRUUHVSRQGLQJ PRODU DEVRLSWLYLW\ RI DERXW / PROfnHP )LQH WXQLQJ RI WKH $PD[ LQ VROXWLRQ FRXOG EH DFKLHYHG E\ FRQWUROOLQJ WKH S+ RI WKH VROXWLRQ DVVXPLQJ WKDW SRO\PHU VROXELOLW\ LQ D VXLWDEOH VROYHQW FDQ EH PDLQWDLQHGf DV LQFRPSOHWH SURORQJDWLRQ ZRXOG OHDG WR D ORZHU H[WHQW RI K\SVRFKURPLF VKLIW 7KH VROXWLRQ HPLVVLRQ UHVXOWV UHYHDOHG D GUDPDWLF LQFUHDVH LQ WKH HPLVVLRQ LQWHQVLW\ IRU WKH SURWRQDWHG SRO\PHU ZKHQ FRPSDUHG WR WKH QHXWUDO 33( PXFK OLNH WKDW VHHQ LQ &KDSWHU IRU WKH 3331(W SRO\PHUV 4XDQWXP \LHOGV ZHUH REWDLQHG IRU HDFK SRO\PHU UHODWLYH WR SHU\OHQH ZLWK D TXDQWXP \LHOG RI UHYHDOLQJ D YDOXH RI RQO\ IRU 33(1(W2&f>@ DQG D GUDPDWLF LQFUHDVH WR IRU WKH SURWRQDWHG 33( 1(W+2&f>@ (DFK SRO\PHU KDV D EOXHJUHHQ VROXWLRQ OXPLQHVFHQFH DW QP IRU 33(1(W2&f>@ DQG QP IRU 33(1(W+2&f>@ 7KH LQFUHDVH LQ TXDQWXP \LHOG LV DWWULEXWHG WR WKH SUHYHQWLRQ RI TXHQFKLQJ RI WKH H[FLWHG VWDWH E\ WKH ORQH SDLU RI HOHFWURQV RQ WKH QLWURJHQ E\ SURWRQDWLRQ 7KH GUDPDWLF FKDQJH LQ HPLVVLRQ ZKHQ WKH DPLQH VLWHV DUH fSURWHFWHGf PDNHV WKHVH SRO\PHUV H[FHOOHQW FDQGLGDWHV IRU + RU DON\ODWLQJ DJHQW VHQVRUV 7DEOH VXPPDUL]HV WKH RSWLFDO SURSHUWLHV IRU WKH 33( 2&f SRO\PHUV

PAGE 109

7DEOH 6XPPDU\ RI RSWLFDO GDWD IRU 33(2&4f W\SH SRO\PHUV 3RO\PHU $EVRUEDQFH A PD[ QPf )LOP &RORU (PLVVLRQ A!PD[ QPf (PLVVLRQ &RORU 6ROXWLRQf 4XDQWXP @ 2UDQJH %OXH*UHHQ 33( 1(W+ 2&f >@ 2UDQJH %OXH*UHHQ M F e ( F R &2 &2 ( /8 2 &' 2 F 4 2 &2 ;f )LJXUH 1RUPDOL]HG 899LV DEVRUSWLRQ DQG VROXWLRQ SKRWROXPLQHVFHQFH IRU 33( 2&f W\SH SRO\PHUV Df 33(1(W+2&f>@ 899LV DEVRUSWLRQ LQ (W2+ Ef 33(1(W2&f>@ 899LV DEVRUSWLRQ LQ &+& Ff 33(1(W+2&f>@ HPLVVLRQ LQ (W2+ Gf 33(1(W2&f>@ HPLVVLRQ LQ &+&,

PAGE 110

7KHUPDO GHSURWRQDWLRQ RI WKH DPLQH VLWHV FDQ RFFXU LI WKH SRO\PHU LV H[SRVHG WR HOHYDWHG WHPSHUDWXUHV WKXV LQGLFDWLQJ D G\QDPLF HTXLOLEULXP DW WKH DPLQH VLWHV 7KLV GHn SURWRQDWLRQ LV HYLGHQFHG LQ WKH 7*$ IRU 33(1(W+2&f>@ VKRZQ LQ )LJXUH ZKHUH DQ LQLWLDO GHJUDGDWLRQ HYHQW VWDUWLQJ DW r& LV REVHUYHG ORVV RI +&f IROORZHG E\ D VWHDG\ GHFOLQH LQ ZHLJKW ZHLJKWb UHPDLQLQJ # r&f 7KH LQLWLDO ZHLJKW ORVV HYHQW LQ WKH GHJUDGDWLRQ RI 33(1(W2&f>@ RFFXUV VOLJKWO\ KLJKHU DW r& IROORZHG E\ D VWHDG\ GHFOLQH LQ ZHLJKW ZHLJKWb UHPDLQLQJ # r&f %RWK SRO\PHUV DUH FRPSOHWHO\ GHJUDGHG E\ D WHPSHUDWXUH RI r& 7HPSHUDWXUH r&f )LJXUH 7*$ WKHUPRJUDPV IRU QHXWUDO DQG SURWRQDWHG 33(2&f XQGHU 1 Df 33(1(W2&f>@ QHXWUDO Ef f§ 33(1(W+2&f>@ SURWRQDWHG

PAGE 111

&RQFOXVLRQV $Q LQWHUHVWLQJ FDWLRQLF SRO\"SKHQ\OHQHHWK\Q\OHQHf 33( 1(W+2&f>@f KDV EHHQ V\QWKHVL]HG E\ DSSOLFDWLRQ RI WKH +HFN&DVVDU 6RQRJDVKLUD+DJLKDUD UHDFWLRQ 8VLQJ WKLV UHDFWLRQ YHU\ KLJK PROHFXODU ZHLJKW VSHFLHV FDQ EH V\QWKHVL]HG DLGHG E\ WKH SUHFLSLWDWLRQ RI DPLQH VDOWV ZKLFK GULYH WKH SRO\PHUL]DWLRQ WR FRPSOHWLRQ :LWK WKH KLJK ULJLGLW\ DQG VROXELOLW\ LVVXHV RI WKHVH 33( V\VWHPV RIWHQWLPHV LW LV PRUH IUXLWIXO WR OLPLW PROHFXODU ZHLJKW ZLWK HQGFDSSLQJ DJHQWV WR LPSURYH VROXELOLW\ DQG DLG LQ PROHFXODU ZHLJKW GHWHUPLQDWLRQ YLD n+ 105 DQDO\VLV 7KH XVH RI 3G33Kf DV FDWDO\VW KHOSV DYRLG VWRLFKLRPHWULF LPEDODQFH SUREOHPV WKDW FDQ RFFXU ZLWK PRQRPHU HTXLYDOHQFLHV ZKHQ 3G,,f FDWDO\VWV DUH XVHG EXW VSHFLDO FDUH PXVW EH WDNHQ LQ WKH KDQGOLQJ RI WKH DLU VHQVLWLYH FDWDO\VW 8VLQJ WKH FRQGLWLRQV GHVFULEHG LQ WKLV FKDSWHU DQG WKH H[SHULPHQWDO VHFWLRQ LQ &KDSWHU WKH QHXWUDO SRO\PHU 33(1(W2&f>@ ZDV LVRODWHG LQ QHDUO\ TXDQWLWDWLYH \LHOG ZLWK VSHFLDO FDUH WDNHQ WR HQVXUH WKH SRO\PHU FKDLQV GLG QRW DJJUHJDWH DQG GHFUHDVH VROXELOLW\ SRVWSUHFLSLWDWLRQ $ QXPEHU DYHUDJH PROHFXODU ZHLJKW RI JPRO ZDV HVWLPDWHG E\ f+ 105 FRUUHVSRQGLQJ WR D GHJUHH RI SRO\PHUL]DWLRQ RI *3& GHWHUPLQDWLRQV RI SRO\GLVSHUVLW\ DQG PROHFXODU ZHLJKWV ZHUH XQVXFFHVVIXO DW WKLV WLPH GXH WR VHYHUDO IDFWRUV 2SWLFDO GDWD KDYH VKRZQ WKDW WKH SRO\PHUV HPLW LQ WKH EOXH JUHHQ UHJLRQ RI WKH YLVLEOH VSHFWUXP LQ VROXWLRQ DQG WKH VROXWLRQ TXDQWXP \LHOG LPSURYHV IURP WR LQ WKH FDVH RI WKH QHXWUDO FRPSDUHG WR WKH SURWRQDWHG SRO\PHU 7KHVH UHVXOWV KDYH RSHQ WKH GRRU IRU FRQWLQXHG UHVHDUFK LQ 33( SRO\PHUV IRU WKH 5H\QROGVf UHVHDUFK JURXS 8VLQJ WKH H[SHULPHQWDO SURWRFROV RXWOLQHG LQ WKLV FKDSWHU IXWXUH ZRUNHUV FDQ IXUWKHU PRGLI\ WKH 33( EDFNERQH VWUXFWXUHV WR LPSURYH VROXELOLW\

PAGE 112

ZLWK WKH XVH RI RWKHU EXON\ fELVf VXEVWLWXHQWV VXFK DV HWK\OKH[\Of DQGRU FUHDWH LQWHUHVWLQJ QHZ PDWHULDOV HVSHFLDOO\ ZLWK WKH V\QWKHVHV RXWOLQHG LQ )LJXUHV WKURXJK )XUWKHUPRUH WKH OHQJWK RI WKH FDUERQ VSDFLQJ LQ WKH VWDUWLQJ PDWHULDO FRXOG EH DGMXVWHG WR XOWLPDWHO\ SURYLGH 33(fV ZLWK DFWLYH HQGJURXSV DW GLIIHULQJ OHQJWKV IURP WKH FRQMXJDWHG SRO\PHU EDFNERQH 6XFK PDWHULDOV ZRXOG EH LQWHUHVWLQJ IRU SRVVLEOH VXUIDFH DGVRUSWLRQ VWXGLHV RU HQHUJ\ WUDQVIHU VWXGLHV WR PHWDOODWHG VSHFLHV FRYDOHQWO\ DWWDFKHG WR WKH FKDLQ HQGV

PAGE 113

&+$37(5 &21&/86,216 3RO\PHU FKHPLVWU\ DQG VFLHQFH RQFH WKRXJKW RI DV PHUHO\ D JUDIWHG EUDQFK RQWR WKH WUHH RI WUDGLWLRQDO FKHPLVWULHV RUJDQLF LQRUJDQLF SK\VLFDOf KDV WDNHQ LWV SODFH DV D IXQGDPHQWDO VFLHQFH RYHU WKH SDVW GHFDGHV 7KH fWUHHf RI SRO\PHU FKHPLVWU\ ZLOO DOZD\V EH URRWHG LQ WKH DERYH PHQWLRQHG FKHPLFDO GLYLVLRQV EXW LW KDV JURZQ WR XQH[SHFWHG KHLJKWV RQ LWV RZQ PHULWV DQG EUDQFKHG LQWR ILHOGV RI VWXG\ KLWKHUWR XQIRUHVHHQ ,W LV ILWWLQJ WKDW PDQ\ RI WRGD\f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fSRO\HOHFWURO\WH HIIHFWff 8VLQJ 6X]XNL 6WLOOH DQG 6RQRJDVKLUD W\SH 3Gf FURVVFRXSOLQJ UHDFWLRQV D VHULHV RI WKUHH GLIIHUHQW SRO\PHU

PAGE 114

EDFNERQHV ZHUH V\QWKHVL]HG >SRO\SSKHQ\OHQHf SRO\"SKHQH\OHQHFF!WKLRSKHQHf DQG SRO\"SKHQH\OHQHHWK\Q\OHQHf@ HDFK ZLWK LWV RZQ GLVWLQJXLVKLQJ SK\VLFDO FKHPLFDO DQG RSWLFDO SURSHUWLHV &KDSWHU RI WKLV GLVVHUWDWLRQ SUHVHQWV WKH H[SHULPHQWDO ZRUN RQ WKH SRO\S SKHQ\OHQHf GHULYDWLYHV 3331(f ZKLFK FRQWDLQ DONR[\DPLQH VLGH FKDLQV WKDW FDQ EH TXDWHPL]HG RU SURWRQDWHG WR JHQHUDWH ZDWHU VROXEOH SRO\PHUV WKDW HPLW EOXH OLJKW ,QLWLDO ZRUN FRQGXFWHG E\ 'U 3HWHU %DODQGD ZDV H[SDQGHG XSRQ WR DOORZ IRU VFDOH XS SURGXFWLRQ DQG HOLPLQDWLRQ RI FRQWDPLQDWLRQ E\ SUHFLSLWDWHG 3Gf PHWDO LQWR WKH SRO\PHU 0RGLILHG 6X]XNL SRO\PHUL]DWLRQ SURWRFROV ZHUH HPSOR\HG LQ WKH YDULRXV 333 1(W V\QWKHVHV WR FRXSOH ELVQHRSHQW\OJO\FROfOSKHQ\OHQHGLERURQDWH ZLWK ELV >1L9GLHWK\ODPLQR@OR[DSURS\OfOGLLRGREHQ]HQH ',1(Wf 7KH XVH RI 3G&3&GSSIf FDWDO\VW ZDV D VXFFHVV LQ DFKLHYLQJ WKH GHVLUHG JRDOV DV D SRO\PHU 3331(WGSSIf>@ RI 0Q JPRO DQG SRO\GLVSHUVLW\ RI EDVHG RQ *3& UHVXOWV YHUVXV SRO\VW\UHQH VWDQGDUGV ZDV UHFRYHUHG IURP PXOWLJUDP VFDOH UHDFWLRQV ZLWKRXW FRQWDPLQDWLRQ IURP EODFN 3Gf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

PAGE 115

6ROXWLRQ DEVRUEDQFH RI WKH EURPRHWKDQH TXDWHPL]HG GHULYDWLYH 3331(W>@f LQ ZDWHU RFFXUUHG DW QP ZLWK FRUUHVSRQGLQJ SKRWROXPLQHVFHQW HPLVVLRQ DW QP 7KH WDQ SRO\PHULF PDWHULDO FRXOG EH HDVLO\ PDQLSXODWHG LQWR WKLQ PXOWLOD\HU /(' GHYLFHV XVLQJ DQ HOHFWURVWDWLF DGVRLSWLRQ WHFKQLTXH 7KHUPRJUDYLPHWULF DQDO\VLV RI WKH TXDWHPL]HG SRO\PHU UHYHDOHG DQ LQLWLDO ZHLJKW ORVV DW r& GXH WR WKH ORVV RI EURPRHWKDQH DQG D VXEVHTXHQW WULHWK\ODPLQH IUDJPHQW DV WKH VLGH FKDLQV ZHUH FOHDYHG ZLWK KHDWLQJ XQGHU 1 7KH QH[W SURJUHVVLRQ LQ WKH UHVHDUFK ZDV WR ORZHU WKH HQHUJ\ RI WKH HPLVVLRQ E\ LQFRUSRUDWLRQ RI WKLRSKHQH XQLWV LQWR WKH SRO\PHU EDFNERQH ,GHDOO\ WKLV FRXOG EH DFKLHYHG XVLQJ D VLPLODU 6X]XNL UHDFWLRQ DV WKDW XVHG IRU WKH 333fV ([SHULPHQWDWLRQ UHYHDOHG WKDW XVH RI D WKLRSKHQH GLERURQDWH HVWHU LQ D 6X]XNL SRO\PHUL]DWLRQ ZDV LQHIIHFWLYH IRU WKH SURGXFWLRQ RI SRO\PHULF PDWHULDOV DV WKH ERURQDWH IXQFWLRQDO JURXSV RQ WKLRSKHQH DUH PXFK PRUH VXVFHSWLEOH WR K\GURO\VLV DQG GHFRPSRVLWLRQ WKDQ WKRVH RQ SKHQ\OHQH XVHG IRU WKH 333 V\QWKHVLV $ 6WLOOH FRXSOLQJ PHWKRGRORJ\ ZDV HPSOR\HG DQG LW ZDV GHWHUPLQHG WKDW GURSZLVH DGGLWLRQ RI ELVWULPHWK\OVWDQQ\OfWKLRSKHQH WR ',1(W LQ '0) ZLWK 3G&O33Kf FDWDO\VW SURGXFHG WKH KLJKHVW PROHFXODU ZHLJKW SRO\PHU337 1(WGURSf>@ ZLWK D 0Q JPRO DQG SRO\GLVSHUVLW\ RI 7KH VRPHZKDW ORZHU PROHFXODU ZHLJKW FDQ EH DWWQEXWHG WR WKH ORZHU UHDFWLYLW\ RI WKH WLQ UHDJHQWV XVHG LQ WKH 6WLOOH UHDFWLRQ DV FRPSDUHG WR WKH ERURQLF UHDJHQWV XVHG LQ WKH 6X]XNL UHDFWLRQ DQG SRVVLEOH PHWK\O WUDQVIHU IURP WKH ELVWULPHWK\OVWDQQ\OfWKLRSKHQH ZKLFK ZRXOG HQGFDS WKH SRO\PHU DQG WHUPLQDWH FKDLQ H[WHQVLRQ 7KH ZDWHU VROXEOH GHULYDWLYH IRUPHG E\ WUHDWPHQW RI WKH QHXWUDO SRO\PHU ZLWK EURPRHWKDQH 3371(WGURSf>@ KDG D VROXWLRQ DEVRUEDQFH LQ ZDWHU DW QP

PAGE 116

ZLWK D FRUUHVSRQGLQJ SKRWROXPLQHVFHQW HPLVVLRQ DW QP SODFLQJ WKH HPLVVLRQ LQ WKH EOXHJUHHQ UHJLRQ RI YLVLEOH OLJKW 7KH 337 SRO\PHUV ZHUH VOLJKWO\ OHVV WKHUPDOO\ VWDEOH WKDQ WKH 333 SRO\PHUV ZLWK LQLWLDO GHJUDGDWLRQ HYHQWV XQGHU 1 RFFXUULQJ DW r& 8QIRUWXQDWHO\ WKH XVH RI 3371(WGURSf>@ LQ HOHFWUROXPLQHVFHQW GHYLFHV DSSHDUV XQOLNHO\ DV LQLWLDO GDWD IURP FROODERUDWLYH HIIRUWV KDYH LQGLFDWHG YHU\ ORZ HPLVVLRQ IURP WKLQ OD\HU GHYLFHV 8QH[SHFWHGO\ D SURPLVLQJ DSSOLFDWLRQ RI WKH SRO\PHU KDV DULVHQ LQYROYLQJ WKH XVH RI 3371(WGURSf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f PDNHV VROXELOLW\ LVVXHV FUXFLDO ZKHQ GHVLJQLQJ WKH SRO\PHU ,W ZDV IRXQG WKDW FRQWUROOLQJ PROHFXODU ZHLJKW YLD HQGFDSSLQJ WR D GHJUHH RI SRO\PHUL]DWLRQ RI DSSUR[LPDWHO\ ZKHQ UHDFWLQJ OGLHWK\Q\OELVQRQ\OR[\fEHQ]HQH ZLWK ',1(W DORQJ ZLWK FDUHIXO SUHFLSLWDWLRQ DQG GU\LQJ ZDV FULWLFDO LQ LVRODWLRQ D VROXEOH QHXWUDO SRO\PHU $ QXPEHU DYHUDJH PROHFXODU ZHLJKW RI JPRO ZDV HVWLPDWHG E\ n+ 105 FRUUHVSRQGLQJ WR D GHJUHH

PAGE 117

RI SRO\PHUL]DWLRQ RI ULQJVf *3& GHWHUPLQDWLRQV RI SRO\GLVSHUVLW\ DQG PROHFXODU ZHLJKWV ZHUH XQVXFFHVVIXO DW WKLV WLPH GXH WR SRO\PHU LQWHUDFWLRQV ZLWK WKH FROXPQ SDFNLQJ PDWHULDO 7KH QHXWUDO 33( W\SH SRO\PHU 33(1(W2&f>@ FRXOG EH GLVVROYHG LQ RUJDQLF VROYHQWV DQG GUDPDWLFDOO\ LQFUHDVHG HPLVVLRQ ZDV REVHUYHG ZKHQ WKH SRO\PHU ZDV GLVVROYHG LQ HWKDQRO RI ORZHUHG S+ 33(1(W+2&f>@ 7KH DFLGLF VROXWLRQ SURWRQDWHV WKH DPLQH VLWHV DQG SUHYHQWV TXHQFKLQJ RI WKH IOXRUHVFHQFH E\ WKH ORQH SDLU RI HOHFWURQV RQ WKH IUHH DPLQH 2SWLFDO GDWD KDYH VKRZQ WKDW WKH SRO\PHUV HPLW LQ WKH EOXH JUHHQ UHJLRQ RI WKH YLVLEOH VSHFWUXP LQ VROXWLRQ QPf DQG WKH VROXWLRQ TXDQWXP \LHOG LPSURYHV IURP WR LQ WKH FDVH RI WKH QHXWUDO FRPSDUHG WR WKH SURWRQDWHG SRO\PHU 7KHUPDO GHJUDGDWLRQ RI 33(1(W+2&f>@ ZDV LQLWLDWHG DW r& XQGHU 1 ORVV RI +&f IROORZHG E\ D VWHDG\ GHFOLQH LQ ZHLJKW b ZHLJKW b OHIW DW r&f &RPSOHWH GHJUDGDWLRQ RFFXUV E\ D WHPSHUDWXUH RI r& 7UHDWPHQW RI WKH QHXWUDO SRO\PHU ZLWK EURPRHWKDQH SURPRWHG LQVROXELOLW\ RI WKH UHVXOWLQJ SDUWLDOO\ TXDWHPL]HG SRO\PHU DQG ZDV WKXV LQHIIHFWLYH LQ SURGXFLQJ D XVHIXO SRO\HOHFWURO\WH 7DNLQJ LQWR DFFRXQW WKH GLVFRYHULHV DQG REVHUYDWLRQV PDGH RYHU WKH FRDUVH RI WKH JUDGXDWH UHVHDUFK LW EHFRPHV RQO\ QDWXUDO WR ORRN DW ZKLFK IDFHWV RI WKH UHVHDUFK VKRXOG FRQWLQXH LQ RUGHU WR SURGXFH WKH PRVW LPSDFW IRU IXWXUH HQGHDYRUV 7KLV GLVVHUWDWLRQ IUDPHV WKH V\QWKHWLF SURWRFROV RI D YDULHW\ RI 3Gf SRO\PHUL]DWLRQV ZLWK WKH PHWKRGRORJLHV H[SODLQHG LQ D PDQQHU WKDW FDQ RQO\ EH JDLQHG IURP KDQGVRQ H[SHULPHQWDWLRQ 7KH LQVLJKWV VKRXOG EH LQYDOXDEOH WR IXWXUH VWXGHQWV LQ WKH 5H\QROGVf UHVHDUFK JURXS WR FRQVWUXFW FRQMXJDWHG SRO\PHUV QRW HYHQ HQYLVLRQHG DW WKLV SRLQW 0RUH GLUHFW LQ QDWXUH IXWXUH ZRUN FRXOG H[WHQG WKH H[SHULPHQWDO SURFHGXUHV WR FRQVWUXFW D

PAGE 118

FRPSOHWH VHW RI FRQMXJDWHG SRO\HOHFWURO\WHV ZLWK EDQGJDSV WKDW YDU\ RYHU ORZHU YLVLEOH HQHUJ\ UHJLRQV VXFK DV DGGLWLRQ RI DQ DONR[\DPLQH VXEVWLWXWHG SRO\S SKHQ\OHQHYLQ\OHQHf 3RO\PHUV WDLORUHG ZLWK VSHFLILF HQHUJ\ DEVRUSWLRQV DQG HPLVVLRQV WKDW FRXOG WUDQVIHU HQHUJ\ WR VSHFLILF PHWDO FHQWHUV FRXOG HDVLO\ EH GHVLJQHG IRU VHQVLQJ RU FKDUJH WUDQVIHU VWXGLHV 7KH JXLGHOLQHV IXWXUH ZRUNHUV VKRXOG IROORZ DUH VLPSOH GHWHUPLQH WKH SURSHUWLHV QHHGHG ZKLFK W\SH RI FRQMXJDWHG SRO\PHU ZLOO PHHW WKH QHHG DQG SHUIRUP UHDFWLRQV

PAGE 119

&+$37(5 (;3(5,0(17$/ 5HDJHQWV DQG 6ROYHQWV $OO UHDJHQWV DQG VROYHQWV ZHUH SXUFKDVHG IURP $OGULFK RU )LVKHU XQOHVV RWKHUZLVH QRWHG 3G FDWDO\VWV ZHUH SXUFKDVHG H[FOXVLYHO\ IURP 6WUHP &KHPLFDO 'LEURPREHQ]HQH DQG fGLEURPRELSKHQ\O $OGULFKf ZHUH UHFU\VWDOOL]HG IURP KRW SHQWDQH DQG WROXHQH 7HWUDK\GURIXUDQ 7+)f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f VSHFWUD ZHUH UHFRUGHG XVLQJ D 9DUDQ &DU\ ( 899LV1,5 VSHFWURSKRWRPHWHU ZLWK PHDVXUHPHQWV WDNHQ DV WKH DYHUDJH RI WKUHH VHSDUDWH VDPSOHV IRU WKH PRODU DEVRUSWLYLHV GDWD SUHVHQWHG IRU SRO\PHUV )OXRUHVFHQFH UHVXOWV ZHUH REWDLQHG ZLWK D 6SH[ )O SKRWRQ FRXQWLQJ IOXRULPHWHU DW URRP WHPSHUDWXUH 7*$ ZDV SHUIRUPHG XQGHU 1 ZLWK D 3HUNLQ(OPHU 7*$ 7KHUPRJUDYLPHWULF $QDO\]HU DW r& SHU PLQXWH XQGHU 1 DWPRVSKHUH *3& UHVXOWV ZHUH REWDLQHG ZLWK D V\VWHP FRQVLVWLQJ RI D :DWHUV 0RGHO SXPS WZR [ PP 3RO\PHU /DERUDWRULHV /LQHDU 0L[HG %HG 3OJHO SP PL[HG&f FROXPQV LQ VHULHV DQG XVLQJ D 6SHFWUDIORZ 7XQDEOH 899LV 'HWHFWRU *DV FKURPDWRJUDSK\ PHDVXUHPHQWV ZHUH SHUIRUPHG RQ D 6KLPDG]X *&$ XWLOL]LQJ D

PAGE 120

PHWHU ORQJ 5HVWHN &RUSRUDWLRQ 57; FURVVERQG b GLSKHQ\Ob GLPHWK\OVLOR[DQH FROXPQ 7KH KHDWLQJ SURILOH XVHG FRQVLVWHG RI KROGLQJ DW r& IRU PLQXWHV KHDWLQJ WR r& DW D UDWH RI r& SHU PLQXWH DQG KROGLQJ DW WKH ILQDO WHPSHUDWXUH IRU PLQXWHV SULRU WR FRROLQJ &KDSWHU GLPHWKR[\OGLLRGREHQ]HQH f $ P/ QHFN URXQG ERWWRP IODVN ZDV FKDUJHG ZLWK GLPHWKR[\EHQ]HQH f J PPROf DQG D VROYHQW V\VWHP FRQVLVWLQJ RI +2 $F +2 +6E\ YROXPH 7KH UHDFWLRQ PL[WXUH ZDV VWLUUHG XQGHU $U XQWLO WKH GLPHWKR[\EHQ]HQH GLVVROYHG FRPSOHWHO\ J PPROf DQG .,2 J PPROf ZHUH DGGHG DQG WKH UHDFWLRQ KHDWHG WR r& RYHUQLJKW 7KH UHDFWLRQ ZDV FRROHG SRXUHG LQWR P/ + DQG D FUXGH RUDQJH VROLG FROOHFWHG 7KH FUXGH VROLG ZDV UHFU\VWDOOL]HG IURP 7+)+2 \LHOGLQJ D OLJKW \HOORZ VROLG J b \LHOGf PS r& OLW PS r&f + 105 0+] &'&f V +f V +f SSP n& 105 0+] &'&,f SSP $QDO &DOHG IRU &J+J2]/ & + )RXQG & + (,/506 FDOFXODWHG IRU &J+J&A/ )RXQG GLLRGRK\GURTXLQRQH ',+4f GLPHWKR[\OGLLRGREHQ]HQH J PPROf ZDV GLVVROYHG LQ P/ GLFKORURPHWKDQH DQG FRROHG LQ D GU\ LFHDFHWRQH EDWK %RURQ WULEURPLGH J PPROf LQ P/ GLFKORURPHWKDQH ZDV DGGHG GURSZLVH YLD DQ DGGLWLRQ IXQQHO WR WKH VROXWLRQ ZLWK VWLUULQJ 7KH UHDFWLRQ PL[WXUH ZDV KHOG DW r& IRU PLQ DQG WKHQ DOORZHG WR ZDUP WR URRP WHPSHUDWXUH RYHUQLJKW 7KH UHDFWLRQ ZDV DGGHG VORZO\ WR P/ RI LFH ZDWHU $ EURZQ SUHFLSLWDWH ZDV FROOHFWHG DQG UHFU\VWDOOL]HG IURP 7+) +2 OHDYLQJ D ZKLWH FU\VWDOOLQH PDWHULDO J b

PAGE 121

\LHOGf PS r& OLW PS r&f + 105 0+] DFHWRQHGf V +f V +f SSP n & 105 0+] DFHWRQHAf SSP $QDO &DOHG IRU &+, & + )RXQG & + (,/506 FDOFXODWHG IRU&+, )RXQG 'LEURPRK\GURTXLQRQH '%+4f $ OLWHU QHFN URXQG ERWWRP IODVN HTXLSSHG ZLWK PDJQHWLF VWLU EDU DGGLWLRQ IXQQHO DQG QLWURJHQ JDV LQOHW DQG RXWOHW WXELQJ ZDV FKDUJHG ZLWK P/ RI JODFLDO DFHWLF DFLG DQG P/ RI PHWK\OHQH FKORULGH +\GURTXLQRQH f J PPROf ZDV DGGHG DQG UHPDLQHG XQGLVVROYHG :LWK YLJRURXV VWLUULQJ HT RI %U J PPROf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f LVSURSDQRO ZDWHU VROXWLRQ $ ZKLWH FU\VWDOOLQH VROLG ZDV UHFRYHUHG J b \LHOGf PS r& OLW PS r&f + 105 0+] '062UIf V +f V +f SSP ELV>:$GLHWK\ODPLQR@OR[DSURS\OfOGLLRGREHQ]HQH ',1(Wf $ QHFN URXQG ERWWRP IODVN ZDV HTXLSSHG ZLWK D UHIOX[ FRQGHQVHU DQG $U JDV LQOHW GLLRGRK\GURTXLQRQH J PPROf FKORURWULHWK\ODPLQH K\GURFKORULGH f J PPROf DQG .&&! J PPROf ZHUH DGGHG WR WKH UHDFWLRQ IODVN

PAGE 122

P/ RI DFHWRQH GULHG RYHU 0J6f ZDV DGGHG DQG WKH UHDFWLRQ VWLUUHG DQG UHIOX[HG $IWHU GD\V D \HOORZ VOXUU\ ZDV SRXUHG LQWR P/ RI + DQG D VROLG SUHFLSLWDWH FROOHFWHG 7KH ILOWUDWH ZDV H[WUDFWHG ZLWK (W P/ [ P/ [ P/ [ f 7KH VROLG SUHFLSLWDWH ZDV GLVVROYHG LQ (W DQG WKH RUJDQLFV FRPELQHG 7KH FRPELQHG (W OD\HUV ZHUH ZDVKHG ZLWK 0 1D2+ P/ [ P/ [ P/ [ f + P/ [ f DQG EULQH P/ [ f 7KH (W OD\HU ZDV GULHG RYHU 0J6 DQG WKH VROYHQW UHPRYHG XQGHU UHGXFHG SUHVVXUH OHDYLQJ D \HOORZLVK ZKLWH VROLG 7KH VROLG ZDV UHFU\VWDOOL]HG WZLFH IURP 0H2+ + J b \LHOGf PS r& + 105 0+] &'&f V +f W +] +f W +] +f T +] +f W +] +f SSP n & 105 0+] &'&f SSP $QDO &DOHG IRU &+L1, & + 1 )RXQG & + 1 )$%+506 0 +fFDOFXODWHG IRU &+L1, )RXQG %LV_91GLHWK\ODPLQR@OR[DSURS\OfOGLEURPREHQ]HQH '%1(Wf $ P/ URXQG ERWWRP IODVN ZLWK PDJQHWLF VSLQ EDU DQG UHIOX[ FRQGHQVHU ZDV FKDUJHG ZLWK DQK\GURXV SRWDVVLXP FDUERQDWH J PPROf FKORURWULHWK\ODPLQH K\GURFKORULGH f J PPROf GLEURPRK\GURTXLQRQH '%+4 J PPROf DQG P/ DFHWRQH GULHG RYHU 0J6 SUHYLRXVO\f 7KH UHDFWLRQ ZDV EURXJKW WR UHIOX[ IRU WKUHH GD\V 7KH UHDFWLRQ PL[WXUH ZDV GLOXWHG ZLWK P/ ZDWHU GLVVROYLQJ DOO VDOWV 7KH SURGXFW ZDV H[WUDFWHG ZLWK HWKHU [ [ P/f DQG WKH FRPELQHG RUJDQLFV ZDVKHG ZLWK 0 1D2+ DTf [ P/f ZDWHU [ P/f DQG EULQH [ P/f 7KH VROXWLRQ ZDV GULHG RYHU 0J6 ILOWHUHG DQG VWULSSHG RI VROYHQW E\ YDFXXP HYDSRUDWLRQ WR \LHOG FUXGH RLO\ VROLGV 7KH FUXGH SURGXFW ZDV UHFU\VWDOOL]HG IURP

PAGE 123

,OO 0H2)/7E2 WZLFH WR JLYH ZKLWH PLFURFU\VWDOOLQH SURGXFW ZKLFK ZDV GULHG LQ YDFXR RYHU &D6 b@ PS r& >+ 105 0+] &'&f SSP V +f W +] +f W +] +f V +f SSP & 105 0+] &'&,f SSP $QDO FDOHG IRU &L+1%U & + 1 )RXQG & + 1 O'LSKHQ\OELV>1$IGLHWK\ODPLQR@OR[DSURS\OfSKHQ\OHQH f $ P/ VLGH DUP YDFXXP IODVN ZLWK PDJQHWLF VWLU EDU ZDV IODPH GULHG XQGHU YDFXXP DQG EDFNILOOHG ZLWK $U JDV P/ RI '0) DQG P/ RI +2 ZHUH DGGHG DQG VSDUJHG ZLWK $U IRU PLQ ',1(W J PPROf SKHQ\OERURQLF DFLG J PPROf DQG 1D+&&UL J PPROf ZHUH DGGHG DQG DOORZHG WR GLVVROYH 3G&KLGSSIf J PPROf ZDV DGGHG LQ RQH SRUWLRQ DQG WKH UHDFWLRQ VWLUUHG ZLWK KHDWLQJ WR r& IRU KRXUV $IWHU FRROLQJ P/ RI (W DQG +2 HDFK ZHUH DGGHG DQG WKH RUJDQLF IUDFWLRQ FROOHFWHG 7KH DTXHRXV OD\HU ZDV H[WUDFWHG ZLWK (W [ P/f DQG WKH FRPELQHG RUJDQLFV ZHUH ZDVKHG ZLWK 0 1D2+ [ P/f +2 [ P/f DQG ILQDOO\ ZLWK EULQH [ P/f 7KH RUJDQLFV ZHUH GULHG RYHU 0J6 DQG WKH VROYHQW UHPRYHG XQGHU YDFXXP UHYHDOLQJ D \HOORZLVK ZKLWH VROLG 7KH SURGXFW ZDV GLVVROYHG LQ 7+) DQG ILOWHUHG WKURXJK D SOXJ RI VLOLFD JHO WR UHPRYH FDWDO\VW FRQWDPLQDWLRQ $IWHU UHPRYDO RI VROYHQW D ZKLWH VROLG ZDV UHFRYHUHG b@ `+ 105 0+] &'&,f SSP G +] +f W +] +f G +] +f V +f W +] +f W +] +f T +] +f W +] +f SSP & 105 0+] &'&,f SSP $QDO FDOHG IRU &+12 &

PAGE 124

+ 1 )RXQG & + 1 )$%+506 0f FDOFXODWHG IRU &+12 )RXQG O'LSKHQ\OELV>1$\9WULHWK\ODPPRQLXP@OR[DSURS\OfSKHQ\OHQH GLEURPLGH f &RPSRXQG J PPROf ZDV GLVVROYHG LQ 7+) DQG VWLUUHG ZLWK P/ RI EURPRHWKDQH IRU GD\V 7KH VROXWLRQ EHFDPH FORXG\ GXULQJ WKH FRXUVH RI WKH UHDFWLRQ $ ZKLWH VROLG J PPROf ZDV FROOHFWHG E\ SUHFLSLWDWLRQ LQWR KH[DQH DQG GULHG LQ YDFXR RYHUQLJKW 7KH QHZ PDWHULDO ZDV KLJKO\ VROXEOH LQ DFHWRQLWULOH DQG ZDWHU LQGLFDWLQJ D VXFFHVVIXO UHDFWLRQ RI WKH QHXWUDO FRPSRXQG b@ r 105 0+] 'f SSP EP +f V +f W +] +f W +] +f T +] +f W +] +f SSP $QDO FDOHG IRU &+12% & + 1 %U )RXQG & + 1 %U )$%+506 0f FDOFXODWHG IRU &+R1%U )RXQG *HQHUDO 3URFHGXUH IRU 6X]XNL 3RO\PHUL]DWLRQ 3UHSDUDWLRQ RI 3RO\^ELV> $A$GLHWK\ODPLQRfOR[DSURS\O@OSKHQ\OHQH`DIOSKHQ\OHQHf >3331(@ 2UJDQLF VROYHQW DQG +2 YYf ZHUH VSDUJHG ZLWK DUJRQ IRU KRXU $ 6FKOHQN IODVN ZLWK D PDJQHWLF VSLQ EDU ZDV FKDUJHG ZLWK '%1(W RU ',1(W ELVQHRSHQW\OJO\FRO SKHQ\OHQHGLERURQDWH f FDUERQDWH EDVH DQG 3G ,,f FDWDO\VW 7KH IODVN ZDV HYDFXDWHG DQG EDFNILOOHG ZLWK DUJRQ WKUHH WLPHV 7KH VROYHQW ZDV DGGHG YLD FDQQXOD WR WKH IODVN DQG WKH UHDFWLRQ ZDV KHDWHG WR r& DQG VWLUUHG IRU DQ DSSURSULDWH DPRXQW RI WLPH 7KH VROXWLRQ ZDV SUHFLSLWDWHG LQWR P/ RI FROG PHWKDQRO DQG FROOHFWHG RQ D JODVV IQW 7KH SRO\PHU ZDV ZDVKHG ZLWK PHWKDQRO WKHQ ZDWHU GULHG LQ DQ DLU VWUHDP WKHQ GULHG LQ YDFXR DW r& RYHUQLJKW 105 DQG RSWLFDO GDWD WKDW DUH LGHQWLFDO IRU DOO 3331(W

PAGE 125

VDPSOHV DUH OLVWHG EHORZ -+ 105 0+] &'&,f EP +f EP +f EP +f EP +f EP +f EP +f SSP & 105 0+] &'&,f SSP 899LV 7+)f $PD[ QP ORJ ePD[ }PD[ QP ORJ ePD[ 89 9LV 0 +&f $PD[ QP ORJ IPD; QP ORJ 9QD; 3/ 7+) ZLWK QP H[FLWDWLRQf $PD[ QP 3/ 0 +& ZLWK QP H[FLWDWLRQf $PD[ QP 3331(W %Uf>@ 5HDJHQWV '%1(W J PPROf ELVQHRSHQW\OJO\FRO SKHQ\OHQHGLERURQDWH J PPROf 1D&&! J PPROf DQG 3G2$Ff PJ PRO bf P/ '0) DQG P/ + ZHUH XVHG DV VROYHQW 5HDFWLRQ WLPH GD\V b@ $QDO FDOHG IRU &+1%URR & + 1 %U )RXQG & + 1 %U *3& &+&, YV 36f 0Q JPROr 03 JPROn 0Z JPROn 0M0f 3331( GSSIf>@ 5HDJHQWV '%1(W J PPROf ELVQHRSHQW\OJO\FRO SKHQ\OHQHGLERURQDWH J PPROf 1D+&&A J PPROf DQG 3G&OGSSIf PJ PRO bf >6WUHP &KHPLFDOV ,QF@ P/ '0) DQG P/ + ZHUH XVHG DV VROYHQW 5HDFWLRQ WLPH GD\V b@ $QDO FDOHG IRU &+1%URR & + 1 %U )RXQG & + 1 %U *3& &+&, YV 36f 0Q JPROr 03 JPROr 0Z JPROn 0M0Q

PAGE 126

3331(,f>@ 5HDJHQWV ',1(W J PPROf ELVQHRSHQW\OJO\FROOSKHQ\OHQH GLERURQDWH J PPROf 1D& J PPROf DQG 3G2$Ff PJ PPROf P/ '0) DQG P/ +2 ZHUH XVHG DV VROYHQW 5HDFWLRQ WLPH KRXUV b@ $QDO FDOHG IRU &+12, & + 1 )RXQG & + 1 *3& &+&, YV 36f 0Q J PRO 03 J PRO 0Z J PRO 0Z0Q 3331( ,f>@ 5HDJHQWV ',1(W J PPROf ELVQHRSHQW\OJO\FROOSKHQ\OHQH GLERURQDWH J PPROf 1D& OJ PPROf DQG 3G2$Ff PJ PPROf P/ '0) DQG P/ +2 ZHUH XVHG DV VROYHQW 5HDFWLRQ WLPH KRXUV b@ $QDO FDOHG IRU &+12, & + 1 )RXQG & + 1 *3& &+&, YV 36f 0Q J PROn 03 J PROn 0Z J PROn 0Z0Q 3RO\LA6ELVAL$A1GLHWK\ODPLQR)OR[DSURS\OOOASKHQ\OHQH-D0Af ELSKHQ\OHQHf >333%31(W>@@ P/ RI 7+) DQG P/ RI +2 ZHUH VSDUJHG ZLWK DUJRQ XQGHU UHIOX[ IRU KRXU $ P/ 6FKOHQN IODVN ZLWK D PDJQHWLF VSLQ EDU ZDV FKDUJHG ZLWK '%1(W J PPROf ELVQHRSHQW\OJO\FRO f GLSKHQ\OHQHGLERURQDWH J PPROf 1D+&&! J PPROf DQG 3G&OGSSIf PJ PRO bf >6WUHP &KHPLFDOV ,QF@ 7KH IODVN ZDV HYDFXDWHG DQG EDFNILOOHG ZLWK DUJRQ WKUHH WLPHV 7KH 7+))/2 VROYHQW VROXWLRQ ZDV DGGHG YLD FDQQXOD WR WKH IODVN DQG WKH UHDFWLRQ ZDV KHDWHG WR r& DQG VWLUUHG IRU GD\V 7KH VROXWLRQ ZDV SUHFLSLWDWHG LQWR P/ RI FROG PHWKDQRO DQG FROOHFWHG RQ D JODVV IULW 7KH SRO\PHU ZDV

PAGE 127

ZDVKHG ZLWK PHWKDQRO WKHQ ZDWHU GULHG LQ DQ DLU VWUHDP WKHQ GULHG LQ YDFXR DW r& RYHUQLJKW b@ $QDO FDOHG IRU &+12 & + 1 )RXQG & + 1 %U 105 0+] &'&,f EP +f EP +f EP +f EP +f EP +f EP +f SSP F 105 0+] &'&,f SSP *3& &+&, YV 36f 0Q JPROn 03 JPROn 0Z JPROn 0Z0Q *3& FXUYH VKDSH SRRUf 899LV 7+)f APD[ QP ORJ APD[ $PD[ QP ORJ ePD[ 3/ 7+) ZLWK QP H[FLWDWLRQf A‘PD[ f§ QP 4XDWHUQL]DWLRQ RI 3RO\PHULF $PLQR)XQFWLRQDOL]HG 3RO\S3KHQ\OHQHffV 6\QWKHVLV SHUFHQW \LHOGV 105 DQG RSWLFDO WUDQVLWLRQV IRU DOO FDWLRQLF 3331(W VDPSOHV ZHUH QHDUO\ LGHQWLFDO WKHUHIRUH H[SHULPHQWDO GHWDLOV DQG FKDUDFWHUL]DWLRQ GDWD DUH OLVWHG RQO\ IRU WKH TXDWHUQL]DWLRQ RI 3331( GSSIf>@ WR WKH FDWLRQLF ZDWHU VROXEOH SRO\PHU 3RO\^ELV>$A$$WULHWK\ODPPRQLXPfOR[DSURS\O@OSKHQ\OHQHWII SKHQ\OHQH` GLEURPLGH >3331(W>@@ $ P/ VLQJOH QHFN URXQG ERWWRP IODVN ZLWK D PDJQHWLF VSLQ EDU ZDV FKDUJHG ZLWK 3331( GSSIf>@ J PPROf DQG VWLUUHG DW URRP WHPSHUDWXUH ZLWK EURPRHWKDQH P/f LQ 7+) P/f LQ D VHDOHG IODVN 7KH SDUWLDOO\ TXDWHPL]HG DPLQH SRO\PHU 3331(W>@ SUHFLSLWDWHG RXW RI VROXWLRQ RYHU WKH FRXUVH RI GD\V 7KH UHDFWLRQ ZDV SRXUHG LQWR DFHWRQH DQG D WDQ SRO\PHU FROOHFWHG RQ D PHGLXP SRURVLW\ JODVV IULW b@ @+ 105 UHVXOWV r+ 105 0+] 'f • EP +f EP +f EP +f

PAGE 128

EP + >WKHR +@@f SSP $QDO FDOHG IRU &+12 &+%U + & + 1 %U )RXQG & + 1 %U 899LV +f $PD[ f§ QP ORJ 9QD[ $PD[ QP ORJ 9QD[ 3/ + ZLWK QP H[FLWDWLRQf ;PD[ QP 3RO\A6ELVWO$M$A$IWULHWK\ODPPRQLXUU2OR[DSURS\OOOASKHQ\OHQHIO fELSKHQ\OHQH` GLEURPLGH >333%31(W>@@ $ P/ VLQJOH QHFN URXQG ERWWRP IODVN ZLWK D PDJQHWLF VSLQ EDU ZDV FKDUJHG ZLWK 333%31(W>@ J PPROf DQG VWLUUHG DW URRP WHPSHUDWXUH ZLWK EURPRHWKDQH P/f LQ 7+) P/f LQ D VHDOHG IODVN 7KH SDUWLDOO\ TXDWHPL]HG DPLQH SRO\PHU 333%31(W>@ SUHFLSLWDWHG RXW RI VROXWLRQ RYHU WKH FRXUVH RI GD\V 7KH UHDFWLRQ ZDV SRXUHG LQWR DFHWRQH DQG D WDQ SRO\PHU FROOHFWHG RQ D PHGLXP SRURVLW\ JODVV IULW b@ $QDO FDOHG IRU &+1%U & + 1 %U )RXQG & + 1 %U &KDSWHU ELVWULPHWK\OVWDQQ\OfWKLRSKHQH f 7KH JHQHUDO SUHSDUDWLRQ RI WKLV R FRPSRXQG IROORZHG OLWHUDWXUH SURFHGXUHV IROORZHG E\ D PRUH ULJRURXV SXULILFDWLRQ QHHGHG IRU SRO\PHUL]DWLRQ TXDOLW\ PRQRPHU 7KH FUXGH UHFRYHUHG SURGXFW ZDV GLVWLOOHG XQGHU YDFXXP 8& # [ PP +Jf DQG WKHQ UHFU\VWDOOL]HG WZLFH IURP SHQWDQH WR \LHOG D ZKLWH FU\VWDOOLQH VROLG
PAGE 129

+f V +f SSP n& 105 0+] &'&f SSP $QDO &DOHG IRU &+66Q & + )RXQG & + )$%+506 0 +fFDOFXODWHG IRU &+66Q )RXQG 7KLRSKHQGL\,GLERURQLF DFLG f 0DJQHVLXP J PPROf ZDV DGGHG WR D QHFN URXQG ERWWRP IODVN ZLWK UHIOX[ FRQGHQVHU DQG DGGLWLRQ IXQQHG OODPH GULHG XQGHU YDFXXP DQG EDFNILOOHG ZLWK $U P/ RI GU\ 7+) ZDV DGGHG WR WKH IODVN GLEURPRWKLRSKHQH J PPROf ZDV GLVVROYHG LQ P/ RI 7+) DQG DGGHG WR WKH DGGLWLRQ IXQQHO 7KH GLEURPR VROXWLRQ ZDV DGGHG VORZO\ ZLWK VWLUULQJ WR WKH PDJQHVLXP DQG EURXJKW WR UHIOX[ IRU KRXUV DIWHU WKH DGGLWLRQ ZDV FRPSOHWH 7KH UHDFWLRQ ZDV WKHQ FRROHG DQG FKLOOHG WR r& 7ULPHWK\O ERUDWH J PPROf ZDV DGGHG GURSZLVH WR WKH *ULJQDUG UHDJHQW DQG DOORZHG WR ZDUP WR 57 RYHUQLJKW (W ZDV DGGHG P/f DQG 0 +& ZDV DGGHG VORZO\ WR GLVVROYH WKH 0J VDOWV 7KH HWKHU OD\HU ZDV FROOHFWHG DQG WKH DTXHRXV OD\HU H[WUDFWHG ZLWK HWKHU [ P/f 7KH FRPELQHG RUJDQLFV ZHUH HYDSRUDWHG OHDYLQJ D VPHOO\ EURZQ RLO 7KH RLO ZDV VXFFHVVIXOO\ SUHFLSLWDWHG LQWR 0 +& DQG D VROLG FROOHFWHG 7KH VROLG ZDV UHFU\VWDOOL]HG IURP + DQG J RI D ZKLWH PDWHULDO ZDV FROOHFWHG b \LHOGf f+ 105 0+] '062 Gf V +f V +f SSP %LVGLPHWK\OWULPHWK\OHQH WKLRSKHQGL\OGLERURQDWH f 7KLRSKHQH GL\OGLERURQLF DFLG f J PPROf QHRSHQW\OJO\FRO J PPROf DQG P/ RI EHQ]HQH ZHUH DGGHG WR D P/ URXQG ERWWRP IODVN HTXLSHG ZLWK D 'HDQ 6WDUN WUDS DQG UHIOX[ FRQGHQVHU 7KH UHDFWLRQ ZDV VWLUUHG DQG UHIOX[HG ZKLOH WKH +EHQ]HQH D]HRWURSH ZDV FROOHFWHG LQ WKH WUDS $IWHU KRXUV WKH UHDFWLRQ ZDV FRROHG GULHG RYHU 0J6 DQG WKH VROYHQW UHPRYHG E\ UHGXFHG SUHVVXUH HYDSRUDWLRQ $ ZKLWH

PAGE 130

VROLG ZDV UHFRYHUHG DQG UHFU\VWDOOL]HG IURP KH[DQH DQG D PLQLPDO DPRXQW RI WROXHQH J b \LHOGf PS r& OLW PS r&f nK 105 0+] &'&f V +f V +f V +f SSP f& 105 0+] &'&f SSP $QDO &DOHG IRU &+6% & + )RXQG & + )$%+506 0 f FDOFXODWHG IRU &+6% )RXQG ELVWRO\OfWKLRSKHQH >6X]XNL WHVW UHDFWLRQV@ f )RU DOO UHDFWLRQV FRPSRXQG J PPROf EURPRWROXHQH J PPROf 1D+&J PPROf DQG PROb 3G&OGSSIf ZHUH XVHG 6ROYHQWV ZHUH YDULHG DPRQJ 7+) '0) DQG WROXHQH LQ D E\ YROXPH UDWLR ZLWK + 5HDFWLRQV ZHUH FRQGXFWHG DW URRP WHPSHUDWXUH 8& RU UHIOX[ HLWKHU DV RQH SRW W\SH UHDFWLRQV RU FRPSRXQG ZDV DGGHG VORZO\ WR WKH UHDFWLRQ P/ RI + DQG P/ RI (W ZHUH DGGHG DIWHU KRXUV 7KH RUJDQLF OD\HU ZDV DQDO\]HG YLD JDV FKURPDWRJUDSK\ DQG SURGXFW LGHQWLW\ GHWHUPLQHG VROHO\ E\ PDVV VSHFWURVFRS\ *&06f 1R IXUWKHU LGHQWLILFDWLRQ RU SXULILFDWLRQ RI WKH UHDFWLRQV ZDV FRQGXFWHG 7DEOH VXPPDUL]HV WKH *&06 UHVXOWV 3RO\^ELV>$U$GLHWK\ODPLQRfOR[DSURS\O@OSKHQ\OHQH`DI WKLHQ\OHQHf 3371(Wf *HQHUDO 3URFHGXUH IRU 6WLOOH 2QH 3RW 6\QWKHVLV $ P/ 6FKOHQN IODVN ZLWK VWLU EDU ZDV FKDUJHG ZLWK ',1(W DQG ELVWULPHWK\OVWDQQ\OfWKLRSKHQH f 7KH IODVN ZDV HYDFXDWHG DQG EDFNILOOHG ZLWK $U WKUHH WLPHV P/ RI DQK\GURXV '0) SUHYLRXVO\ VSDUJHG ZLWK $U IRU PLQ ZDV DGGHG WR WKH UHDFWLRQ IODVN YLD V\ULQJH 7KH UHDFWLRQ PL[WXUH ZDV VWLUUHG DQG KHDWHG WR r& DOORZLQJ DOO PRQRPHUV WR GLVVROYH 3G&O33Kf ZDV DGGHG LQ RQH SRUWLRQ DQG WKH UHDFWLRQ KHDWHG DW r& IRU D YDULDEOH QXPEHU RI KRXUV

PAGE 131

7KH '0) VROXWLRQ ZDV FRQFHQWUDWHG WR a P/ DQG SUHFLSLWDWHG LQWR P/ 0H2+ $ GDUN UHG VROLG ZDV FROOHFWHG RQ D PHGLXP SRURVLW\ JODVV IULW DQG VXEVHTXHQWO\ H[WUDFWHG ZLWK 0H2+ IRU KRXUV DFHWRQH IRU KRXUV DQG WKHQ FROOHFWHG E\ H[WUDFWLRQ ZLWK FKORURIRUP YLD 6R[KOHW H[WUDFWLRQf 7KH FKORURIRUP VROXEOH IUDFWLRQ ZDV FROOHFWHG E\ f L HYDSRUDWLRQ RI WKH VROYHQW DQG GULHG LQ YDFXR DW & RYHUQLJKW + 105 0+] &'&f EP +f EP +f EP +f EP +f EP +f EP +f SSP fF 105 0+] &'&f SSP 899LV 7+)f PD[ QP ORJ ePD[ 3/ 7+) ZLWK QP H[FLWDWLRQf ;PD[ QP 3371(Wf>@ 5HDFWLRQ WLPH RI KRXUV 5HDJHQWV ',1(W J PPROf ELVWULPHWK\OVWDQQ\OfWKLRSKHQH f J PPROf DQG PJ RI 3G&O33Kf PPROf J RI SRO\PHU ZDV UHFRYHUHG b \LHOGf $QDO FDOHG IRU &+126, & + 1 )RXQG & + 1 *3& 7+) YV 36f 0f J PROn 03 J PROn 0f J PROn 0M0Q 3371(Wf>@ 5HDFWLRQ WLPH RI KRXUV 5HDJHQWV ',1(W J PPROf ELVWULPHWK\OVWDQQ\OfWKLRSKHQH f J PPROf DQG PJ RI 3G&O33Kf PPROf J RI SRO\PHU ZDV UHFRYHUHG b \LHOGf $QDO FDOHG IRU &+126, & + 1 )RXQG & + 1 *3& 7+) YV 36f 0f J PROn 03 J PROn 0f J PROn 0M0Q

PAGE 132

3371(Wf>@ 5HDFWLRQ WLPH RI KRXUV 5HDJHQWV ',1(W J PPROf ELVWULPHWK\OVWDQQ\OfWKLRSKHQH f J PPROf DQG PJ RI 3G&O33Kf PPROf J RI SRO\PHU ZDV UHFRYHUHG b \LHOGf $QDO FDOHG IRU &+16,RR & + 1 )RXQG & + 1 *3& 7+) YV 36f 0Q J PROn 03 J PROn 0f J PROn 0M0f 3URFHGXUH IRU 6WLOOH 'URS ZLVH 6\QWKHVLV 3371(W GURSf>@ $ P/ 6FKOHQN IODVN ZLWK VWLU EDU ZDV FKDUJHG ZLWK ',1(W J PPROf PJ RI 3G&O33Kf PPROf DQG P/ RI DQK\GURXV '0) SUHYLRXVO\ VSDUJHG ZLWK $U IRU PLQ 7KH VROXWLRQ ZDV ZDUPHG WR r& ELVWULPHWK\OVWDQQ\OfWKLRSKHQH f J PPROf ZDV GLVVROYHG LQ P/ RI '0) DQG DGGHG WR D P/ DGGLWLRQ IXQQHO DWWDFKHG WR WKH 6FKOHQN IODVN &RPSRXQG ZDV DGGHG GURSZLVH RYHU WKH FRXUVH RI KRXUV 7KH UHDFWLRQ PL[WXUH ZDV KHOG DW r& IRU KRXUV 7KH '0) VROXWLRQ ZDV FRQFHQWUDWHG WR a P/ DQG SUHFLSLWDWHG LQWR P/ 0H2+ $ GDUN UHG VROLG ZDV FROOHFWHG RQ D PHGLXP SRURVLW\ JODVV IULW DQG VXEVHTXHQWO\ H[WUDFWHG ZLWK 0H2+ IRU KRXUV DFHWRQH IRU KRXUV DQG WKHQ FROOHFWHG E\ H[WUDFWLRQ ZLWK FKORURIRUP YLD 6R[KOHW H[WUDFWLRQf 7KH FKORURIRUP VROXEOH IUDFWLRQ ZDV FROOHFWHG E\ HYDSRUDWLRQ RI WKH VROYHQW DQG GULHG LQ YDFXR DW r& RYHUQLJKW J RI SRO\PHU ZDV UHFRYHUHG b \LHOGf + 105 0+] &'&f EP +f EP +f EP +f EP +f EP +f EP +f SSP f& 105 0+] &'&f SSP $QDO FDOHG IRU &+16,RR& + 1 )RXQG & + 1

PAGE 133

, *3& 7+) YV 36f 0Q J PROn 03 J PRO 0Z J PRO 0M0Q 3URFHGXUH IRU 6X]XNL 'URSZLVH 6\QWKHVLV 3371(WL 6X]f>@ $ P/ 6FKOHQN IODVN ZLWK VWLU EDU ZDV FKDUJHG ZLWK ',1(W J PPROf PJ RI 3G&KLGSSIf PPROf DQG 1D+& J PPROf P/ '0) DQG P/ RI +2 SUHYLRXVO\ VSDUJHG ZLWK $U IRU PLQ ZHUH WKHQ DGGHG 7KH VROXWLRQ ZDV ZDUPHG WR r& &RPSRXQG J PPROf ZDV GLVVROYHG LQ P/ RI '0) DQG DGGHG WR D P/ DGGLWLRQ IXQQHO DWWDFKHG WR WKH 6FKOHQN IODVN ZDV DGGHG GURSZLVH RYHU WKH FRXUVH RI KRXUV 7KH UHDFWLRQ PL[WXUH ZDV KHOG DW r& IRU KRXUV 7KH VROXWLRQ ZDV FRQFHQWUDWHG WR a P/ DQG SUHFLSLWDWHG LQWR P/ 0H2+ $ OLJKW UHG VROLG ZDV FROOHFWHG RQ D PHGLXP SRURVLW\ JODVV IULW DQG VXEVHTXHQWO\ H[WUDFWHG ZLWK 0H2+ IRU KRXUV DFHWRQH IRU KRXUV DQG WKHQ FROOHFWHG E\ H[WUDFWLRQ ZLWK FKORURIRUP YLD 6R[KOHW H[WUDFWLRQf 7KH FKORURIRUP VROXEOH IUDFWLRQ ZDV FROOHFWHG E\ HYDSRUDWLRQ RI WKH VROYHQW DQG GULHG LQ YDFXR DW r& RYHUQLJKW J RI SRO\PHU ZDV UHFRYHUHG b \LHOGf + 105 0+] &'&f EP +f EP +f EP +f EP +f EP +f EP +f SSP $QDO FDOHG IRU &+126 & + 1 )RXQG & + 1 899LV 7+)f ;PD[ QP ORJ PD[ *3& UHVXOWV VKRZHG D QRQSRO\PHULF GLVWULEXWLRQ DQG YHU\ ORZ PROHFXODU ZHLJKW VSHFLHV *HQHUDO 4XDWHUQL]DWLRQ 3URFHGXUH 1HXWUDO DONR[\DPLQH FRQWDLQLQJ SRO\PHUV ZHUH VWLUUHG DW URRP WHPSHUDWXUH ZLWK DQ H[FHVV RI EURPRHWKDQH LQ D PLQLPDO DPRXQW RI 7+) XQGHU $U ZLWK VWLUULQJ 7KH SDUWLDOO\ TXDWHPL]HG DPLQH SRO\PHUV EHJDQ WR SUHFLSLWDWH RXW RI VROXWLRQ EHWZHHQ GD\V DW URRP WHPSHUDWXUH 7KH TXDWHPL]HG

PAGE 134

SRO\PHU VROXWLRQ ZDV SUHFLSLWDWHG LQWR DFHWRQH FROOHFWHG RQ D JODVV IULW ZDVKHG WKRURXJKO\ ZLWK DFHWRQH DQG GULHG LQ YDFXR DW r& RYHUQLJKW 3RO\^ELV>L999WULHWK\ODPPRQLXPfOR[DSURS\O@OSKHQ\OHQHDI WKLHQ\OHQH` GLEURPLGH 3371(Wf r+ 105 0+] 'f EP +f EP +f EP +f EP +f EP +f EP +f SSP 899LV +2f ;PD[ QP ORJ PD[ 3/ +2 ZLWK QP H[FLWDWLRQf ;PD[ QP 3371(Wf>@ $QDO FDOHG IRU &+16,RRr &+%U & + 1 %U )RXQG & + 1 %U 3371(WGURSf>@ $QDO FDOHG IRU &+16,RRr &+%U & + 1 %U )RXQG & + 1 %U &KDSWHU *HQHUDO 3URFHGXUH IRU :LOOLDPVRQ (WKHULILFDWLRQ RI +\GURTXLQRQH $ VXVSHQVLRQ RI SRZGHUHG .2+ LQ P/ RI '062 ZDV DGGHG WR D GU\ P/ WKUHH QHFN URXQG ERWWRP IODVN DQG VWLUUHG IRU KRXU +\GURTXLQRQH DQG WKH DON\OEURPLGH ZHUH DGGHG LQ RQH SRUWLRQ XQGHU D VWHDG\ VWUHDP RI $U 7KH UHDFWLRQV ZHUH VWLUUHG DQG KHDWHG WR r& IRU KRXUV 8SRQ FRROLQJ WKH UHDFWLRQ PL[WXUH ZDV SRXUHG LQWR P/ RI + 7KH DTXHRXV PL[WXUH ZDV H[WUDFWHG ZLWK KH[DQH [ f DQG WKH FRPELQHG RUJDQLFV ZDVKHG ZLWK 0 1D2+ P/ [ P/ [ P/ [ f + P/ [ f DQG EULQH P/ [ f $IWHU GU\LQJ RYHU 0J6 WKH VROYHQW ZDV UHPRYHG E\ UHGXFHG SUHVVXUH HYDSRUDWLRQ

PAGE 135

%LVKH[\OR[\fEHQ]HQH f 5HDJHQWV +\GURTXLQRQH J PPROf KH[\OEURPLGH J PPROf DQG .2+ J PPROf 3URGXFW ZDV FROOHFWHG DV D FUXGH EURZQLVK VROLG DQG ZDV UHFU\VWDOOL]HG IURP HWKDQRO JLYLQJ J RI D ZKLWH FU\VWDOOLQH PDWHULDO b \LHOGf PS r& + 105 0+] &'&f V +f W +f P +f EP +f W +f SSP F 105 0+] &'&f SSP %LVQRQ\R[\fEHQ]HQH f 5HDJHQWV +\GURTXLQRQH J PPROf QRQ\OEURPLGH J PPROf DQG .2+ J PPROf 3URGXFW ZDV FROOHFWHG DV D FUXGH EURZQLVK VROLG DQG ZDV UHFU\VWDOOL]HG IURP HWKDQRO JLYLQJ J RI D ZKLWH FU\VWDOOLQH PDWHULDO b \LHOGf PS r& + 105 0+] &'&f V +f W +f P +f EP +f W +f SSP F 105 0+] &'&f SSP *HQHUDO SURFHGXUH IRU WKH LRGLQDWLRQ RI GLDONR[\EHQ]HQHV $ P/ QHFN URXQG ERWWRP IODVN ZDV FKDUJHG ZLWK GLDONR[\EHQ]HQH DQG D VROYHQW V\VWHP FRQVLVWLQJ RI +2$F +2 +62 E\ YROXPH &+&, ZDV DGGHG XQWLO WKH GLDONR[\EHQ]HQH GLVVROYHG DQG ., ZHUH DGGHG DQG WKH UHDFWLRQ KHDWHG WR r& RYHUQLJKW 7KH UHDFWLRQ ZDV FRROHG SRXUHG LQWR P/ +2 DQG H[WUDFWHG ZLWK FKORURIRUP [ f 7KH FRPELQHG RUJDQLFV ZHUH GULHG RYHU 0J6&/ DQG WKH VROYHQW HYDSRUDWHG 3XULILFDWLRQ ZDV DFFRPSOLVKHG E\ UHFU\VWDOOL]DWLRQ RU FROXPQ FKURPDWRJUDSK\ GHSHQGLQJ RQ WKH FRPSRXQG %LVKH[\OR[\fGLLRGREHQ]HQH f 5HDJHQWV %LVKH[\OR[\fEHQ]HQH J PPROf J PPROf DQG .,2 J

PAGE 136

PPROf 3URGXFW ZDV FROOHFWHG DV D FUXGH UHGEURZQ VROLG DQG SXULILHG E\ UHFU\VWDOOL]DWLRQ IURP HWKDQRO \LHOGLQJ J RI D ZKLWH FU\VWDOOLQH VROLG b \LHOGf PS r& + 105 0+] &'&f V +f W +f P +f EP +f W +f SSP f& 105 0+] &'&f SSP $QDO &DOHG IRU &LJ+]J&A & + )RXQG & + 1 )$%+506 0fFDOFXODWHG IRU &+JO )RXQG O%LVQRQ\,R[\fGLLRGREHQ]HQH f 5HDJHQWV %LVQRQ\OR[\fEHQ]HQH J PPROf J PPROf DQG .,2 J PPROf 3URGXFW ZDV FROOHFWHG DV D FUXGH UHGEURZQ VROLG DQG SXULILHG E\ UHFU\VWDOOL]DWLRQ IURP HWKDQRO \LHOGLQJ J RI D ZKLWH FU\VWDOOLQH VROLG b \LHOGf PS r& + 105 0+] &'&f V +f W +f P +f EP +f W +f SSP f& 105 0+] &'&f SSP $QDO &DOHG IRU &+2, & + )RXQG & + )$%+506 0fFDOFXODWHG IRU &+2, )RXQG *HQHUDO 3URFHGXUH IRU WKH 6RQRJDVKLUD FRXSOLQJ RI WULPHWK\OVLO\ODFHW\OHQH WR GLLRGREHQ]HQHV 7KH DSSURSULDWH GLLRGREHQ]HQH 3G&O33Kf DQG &XO ZHUH DGGHG WR D GU\ P/ VLGHDUP IODVN XQGHU DUJRQ 'U\ (W1 ZDV DGGHG WR WKH UHDFWLRQ YLD FDQQXOD a P/f 7KH UHDFWLRQ PL[WXUH ZDV VWLUUHG XQWLO UHDJHQWV KDYH GLVVROYHG DQG HTXLYDOHQWV RI WULPHWK\OVLO\ODFHW\OHQH DUH DGGHG LQ RQH SRUWLRQ 7KH UHDFWLRQ ZDV KHDWHG WR r& DQG VWLUUHG RYHUQLJKW $IWHU FRROLQJ WKH UHDFWLRQ ZDV ILOWHUHG WR UHPRYH

PAGE 137

DPPRQLXP VDOWV DQG SDVVHG WKURXJK D VLOLFD JHO SOXJ XVLQJ DQ DSSURSULDWH VROYHQW $IWHU UHPRYDO RI VROYHQW WKH VROLGV ZHUH UHF\UVWDOOL]HG WZLFH IURP PHWKDQRO RU HWKDQRO %LVWULQLHWK\VLO\OfHWK\Q\OfEHQ]HQH f 5HDJHQWV GLLGREHQ]HQH J PPROf WULPHWK\OVLO\ODFHW\OHQH J PPROf 3G&O33Kf J PPROf DQG &XO J PPROf 3URGXFW ZDV FROOHFWHG DV D FUXGH EODFN VROLG DQG SXULILHG E\ FROXPQ FKURPDWRJUDSK\ RQ VLOLFD JHO KH[DQHV&+&Of IROORZHG E\ UHFU\VWDOOL]DWLRQ IURP 0H2+ JLYLQJ ZKLWH FU\VWDOV J b \LHOGf PS 8& + 105 0+] &'&f V +f V +f SSP n & 105 0+] &'&f SSP $QDO &DOHG IRU &+6L & + )RXQG & + )$%+506 0f FDOFXODWHG IRU &+6 )RXQG %LVWULPHWK\VLO\,fHWK\Q\OfELVKH[\OR[\fEHQ]HQH f 5HDJHQWV ELVKH[\OR[\fGLLRGREHQ]HQH J PPROf WULPHWK\OVLO\ODFHW\OHQH J PPROf 3G&O33Kf J PPROf DQG &XO J PPROf 3URGXFW ZDV FROOHFWHG DV D FUXGH EODFN VROLG DQG SXULILHG E\ FROXPQ FKURPDWRJUDSK\ RQ VLOLFD JHO KH[DQHV&))&)f IROORZHG E\ UHFU\VWDOOL]DWLRQ IURP 0H2+ JLYLQJ IDLQW \HOORZ FU\VWDOV J b \LHOGf + 105 0+] &'&f V +f W +f P +f P +f P +f W +f V +f SSP nnF 105 0+] &'&,f SSP $QDO &DOHG IRU &+6L & + )RXQG & + )$%+506 0fFDOFXODWHG IRU &+26 )RXQG %LVWULPHWK\VLO\OfHWK\Q\OfELVQRQ\OR[\fEHQ]HQH f 5HDJHQWV ELVQRQ\OR[\fGLLRGREHQ]HQH J PPROf WULPHWK\OVLO\ODFHW\OHQH J

PAGE 138

PPROf 3G&O33Kf J PPROf DQG &XO J PPROf 3URGXFW ZDV FROOHFWHG DV D FUXGH UHG VROLG DQG SXULILHG E\ FROXPQ FKURPDWRJUDSK\ RQ VLOLFD JHO WROXHQHf IROORZHG E\ UHFU\VWDOOL]DWLRQ IURP HWKDQRO JLYLQJ IDLQW \HOORZ FU\VWDOV J b \LHOGf + 105 0+] &'&f V +f W +f P +f P +f W +f V +f SSP n& 105 0+] &'&f SSP $QDO &DOHG IRU &+26 & + )RXQG & + )$%+506 0f FDOFXODWHG IRU )RXQG *HQHUDO 3URFHGXUH IRU WKH UHPRYDO RI WULPHWK\OVLO\O JURXSV 7KH DSSURSULDWH ELVWULPHWK\VLO\OfHWK\Q\Of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f 5HDJHQWV OELVWULPHWK\VLO\OfHWK\Q\OfEHQ]HQH J PPROf 6ROLG SURGXFW ZDV UHFU\VWDOOL]HG IURP 0H2+ DQG YDFXXP VXEOLPHG WR SURGXFH J RI D ZKLWH VROLG LQ b \LHOG + 105 0+] &'&f V +f V +f SSP nF 105 0+] &'&f SSP $QDO &DOHG IRU &+ & + )RXQG & + )$%+506 0f FDOFXODWHG IRU <+ )RXQG

PAGE 139

GLHWK\Q\OELVKH[\OR[\fEHQ]HQH f 5HDJHQWV ELVWULPHWK\VLO\OfHWK\Q\OfELVKH[\OR[\fEHQ]HQH J PPROf 6ROYHQW ZDV UHPRYHG WR JLYH D \HOORZ FUXGH PDWHULDO ZKLFK ZDV SDVVHG WKURXJK D VLOLFD JHO FROXPQ KH[DQHV&+&Of DQG FU\VWDOOL]HG IURP KH[DQH UHVXOWLQJ LQ FROOHFWLRQ RI J RI D OLJKW \HOORZ PDWHULDO b \LHOGf + 105 0+] &'&f V +f W +f V +f P +f P +f W +f SSP n& 105 0+]&'&f SSP $QDO &DOHG IRU &+2 & + )RXQG & + )$%+506 0fFDOFXODWHG IRU &+2 )RXQG GLHWK\Q\OELVQRQ\OR[\fEHQ]HQH f 5HDJHQWV ELVWULPHWK\VLO\OfHWK\Q\OfELVQRQ\OR[\fEHQ]HQH J PPROf $IWHU H[WUDFWLRQV VROYHQW ZDV UHPRYHG WR JLYH D FUXGH \HOORZ PDWHULDO ZKLFK ZDV FU\VWDOOL]HG IURP KH[DQH WR JLYH J RI D OLJKW \HOORZ PDWHULDO b \LHOGf + 105 0+] &'&f V +f W +f V +f P +f P +f W +f SSP nn& 105 0+] &'&f SSP $QDO &DOHG IRU &+2 & + )RXQG & + )$%+506 0fFDOFXODWHG IRU&+ )RXQG &RPSRXQGV 6HH UHIHUHQFH F IRU FRPSOHWH V\QWKHWLF GHWDLOV %LVEURPRKH[\OfOGLLRGREHQ]HQH f $ P/ QHFN URXQG ERWWRP IODVN ZDV FKDUJHG ZLWK FRPSRXQG J PPROf DQG D VROYHQW V\VWHP FRQVLVWLQJ RI +2$F +2 +6&!E\ YROXPH &+&, ZDV DGGHG XQWLO FRPSRXQG ZDV GLVVROYHG J PPROf DQG ., J PPROf ZHUH DGGHG DQG

PAGE 140

WKH UHDFWLRQ KHDWHG WR r& RYHUQLJKW 7KH UHDFWLRQ ZDV FRROHG SRXUHG LQWR P/ + DQG H[WUDFWHG ZLWK FKORURIRUP [ f 7KH FRPELQHG RUJDQLFV ZHUH GULHG RYHU 0J6 DQG WKH VROYHQW HYDSRUDWHG 3XULILFDWLRQ RI WKH FUXGH EURZQ VROLG ZDV DFFRPSOLVKHG YLD UHFU\VWDOOL]DWLRQ IURP 0H2+ DQG D PLQLPDO DPRXQW RI DFHWRQH J b \LHOGf PS r& + 105 0+] &'&f V +f W +f W +f P +f P +f SSP n& 105 0+] &'&f SSP $QDO &DOHG IRU &+%UO & + )RXQG & + )$% +506 0fFDOFXODWHG IRU &+%U, )RXQG %LVSKHQR[\KH[\OfOGLLRGREHQ]HQH f $ VROXWLRQ RI FRPSRXQG J PPROf LQ GU\ WROXHQH P/f ZDV DGGHG VORZO\ WR D VWLUUHG VROXWLRQ RI SKHQRO J PPROf VRGLXP UEXWR[LGH J PPROf DQG SRWDVVLXP LRGLGH FDWDO\WLFf LQ DQK\GURXV '0) P/f 7KH PL[WXUH ZDV VWLUUHG DQG UHIOX[HG IRU KRXUV :DWHU ZDV DGGHG P/f DQG WKH RUJDQLF OD\HU VHSDUDWHG RII ZLWK WKH DTXHRXV OD\HU EHLQJ H[WUDFWHG ZLWK EHQ]HQH [ O22P/f 7KH FRPELQHG RUJDQLF OD\HUV ZHUH ZDVKHG ZLWK 0 1D2+ [ O22P/f ZDWHU [ P/f DQG EULQH [ P/f DQG GULHG RYHU 0J6 7KH VROYHQW ZDV UHPRYHG LQ YDFXR DQG WKH REWDLQHG FUXGH SURGXFW ZDV UHFU\VWDOOL]HG IURP KH[DQH J b \LHOGf PS r& + 105 0+] &'&f V +f P +f P +f W +f W +f P +f P +f SSP F 105 0+] &'&f SSP $QDO &DOHG IRU &R+, & + )RXQG & + )$%+506 0f FDOFXODWHG IRU &R+, )RXQG

PAGE 141

*HQHUDO 6RQRJDVKLUD 3RO\PHUL]DWLRQ 3URFHGXUH IRU 3RO\" SKHQ\OHQHHWK\Q\OHQHffV 33(1(W5f 7KH DSSURSULDWH GLHWK\Q\O FRPSRXQG HTXLYDOHQWVf ',1(W 3G33Kf PRObf DQG &XO PRObf DUH SODFHG LQ D GU\ P/ 6FKOHQN IODVN DQG HYDFXDWHG DQG EDFNILOOHG ZLWK $U WKUHH WLPHV $ E\ YROXPH VROXWLRQ RI WKRURXJKO\ VSDUJHG WROXHQH DQG GLLVRSURS\ODPLQH VROYHQW V\VWHP ZDV DGGHG WR WKH UHDFWLRQ YLD V\ULQJH LQ DQ DPRXQW PDNLQJ WKH UHDFWLRQ 0 LQ ',1(W 7KH UHDFWLRQ ZDV KHDWHG WR r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f GLHWK\Q\OEHQ]HQH f J PPROf &XO PJ PPROfDQG PJ RI 3G33Kf PPROf J RI SRO\PHU ZDV UHFRYHUHG b \LHOGf $QDO FDOHG IRU &+1 & + 1 )RXQG & + 1 7KH SRO\PHU SUHFLSLWDWHG GXULQJ WKH FRDUVH RI WKH UHDFWLRQ DQG ZDV LQVROXEOH DIWHU FROOHFWLRQ DQG GU\LQJ 3RO\PHU 33(1(W2&>@ 5HDJHQWV ',1(W J PPROf GLHWK\Q\OELVKH[\OR[\fEHQ]HQH f J PPROf &XO PJ PPROf DQG PJ RI 3G33Kf PPROf J RI SRO\PHU ZDV UHFRYHUHG b \LHOGf $QDO FDOHG IRU &+12 & + 1 )RXQG & +

PAGE 142

1 $ VPDOO SRUWLRQ RI WKH SRO\PHU SUHFLSLWDWHG GXULQJ WKH UHDFWLRQ PJ RI VROXEOH PDWHULDO FRXOG EH H[WUDFWHG ZLWK DQ H[FHVV RI ERLOLQJ FKORURIRUP DIWHU SUHFLSLWDWLRQ DQG GU\LQJ 3RO\PHU 33(1(2& +LJKf>@ 5HDJHQWV ',1(W J PPROf OGLHWK\Q\OELVQRQ\OOR[\fEHQ]HQH f J PPROf &XO PJ PPROfDQG PJ RI 3G33Kf PPROf J RI SRO\PHU ZDV UHFRYHUHG b \LHOGf $QDO FDOHG IRU &+12 & + 1 )RXQG & + 1 7KH SRO\PHU IRUPHG D fJHOf GXULQJ WKH UHDFWLRQ ZKLFK ZDV GLVVROYHG ZLWK H[FHVV FKORURIRUP $IWHU SUHFLSLWDWLRQ ZDVKLQJ DQG GU\LQJ WKH SRO\PHU ZDV FRPSOHWHO\ LQVROXEOH LQ DQ\ FRPPRQ RUJDQLF ERLOLQJ VROYHQW 3RO\PHU 33(1(2& f>@ 5HDJHQWV ',1(W J PPROf OGLHWK\Q\OELVQRQ\OOR[\fEHQ]HQH f J PPROf LRGREHQ]HQH PJ PPROf &XO PJ PPROf DQG PJ RI 3G33Kf PPROf J RI SRO\PHU ZDV UHFRYHUHG b \LHOGf $QDO FDOHG IRU &+12 & + 1 )RXQG & + 1 7KH SRO\PHU UHPDLQHG VROXEOH GXULQJ WKH UHDFWLRQ DQG XSRQ SUHFLSLWDWLRQ DQG FRPSOHWH GU\LQJ D VPDOO DPRXQW RI PDWHULDO ZDV VROXEOH LQ FKORURIRUP 7KH H[SHULPHQW ZDV FRQGXFWHG D VHFRQG WLPH XVLQJ WKH FRQGLWLRQV DERYH DQG WKH SRO\PHU ZDV FROOHFWHG YLD JUDYLW\ ILOWUDWLRQ WKURXJK FRDUVH ILOWHU SDSHU DQG RQO\ DLU GULHG 7KH fVROYDWHGf SRO\PHU GLVSOD\HG PXFK JUHDWHU VROXELOLW\ DOORZLQJ IRU PRUH FRPSOHWH DQDO\VHV DQG FRQYHUVLRQ WR WKH FDWLRQLF SRO\HOHFWURO\WH -+ 105 0+] &'&,f EV +f EV +f EP +f EP +f EV +f EP +f EP +f EP +f EP +f EP +f EW +f (QGJURXS P +f SSP & 105 0+] &'&,f

PAGE 143

SSP $QDO FDOHG IRU &+R1 & + 1 )RXQG & + 1 899LV &+&f $PD[ QP ORJ UPD[ 89 9LV 0 +& LQ (W2+ 33(1(W+2&f>@f ƒPD[ QP ORJ ePD[ 3/ &+&Ef $PD[ QP 4XDQWXP @f $PD[ QP 4XDQWXP @ 33(1(W2&f>@ J PPROf ZDV GLVVROYHG LQ PO RI &+&, DQG DQ H[FHVV RI EURPRHWKDQH ZDV DGGHG P/f 7KH UHDFWLRQ ZDV KHDWHG WR r& DQG VWLUUHG IRU GD\V (DFK GD\ a P/ RI DFHWRQLWULOH ZDV DGGHG WR HQVXUH WKDW WKH SRO\HOHFWURO\WH EHLQJ IRUPHG UHPDLQHG LQ VROXWLRQ 2YHU WKH FRDUVH RI WKH UHDFWLRQ D VZROOHQ RUDQJH PDWHULDO GLG SUHFLSLWDWH IURP WKH UHDFWLRQ 7KH UHDFWLRQ ZDV FRROHG FRQFHQWUDWHG DQG DGGHG WR P/ RI 7+) PJ RI DQ RUDQJH VROLG ZDV UHFRYHUHG b \LHOGf 7KH PDWHULDO ZDV SRRUO\ VROXEOH LQ HWKDQRO DQG LQVROXEOH LQ ZDWHU FKORURIRUP DQG 7+) 7KH SRUWLRQ RI PDWHULDO VROXEOH LQ HWKDQRO GLVSOD\HG RSWLFDO DEVRUEDQFHV VLPLODU WR WKDW RI 33(1(W+2&f>@ $QDO FDOHG IRU &R+R1%U & + 1 %U )RXQG & + 1 %U

PAGE 144

&+$37(5 5()(5(1&(6 6WDXGLQJHU + 'LH +RFKPROHFXODUHQ 6SULQJHU9HUODJ %HUOLQ ,WR 7 6KLUDNDZD + ,NHGD 6 3RO\P 6FL 3RO\P &KHP (G /LHVHU :HJQHU ) 0OOHU : (QNHOPDQQ 9 0H\HU :0DNURPRO &KHP 5DS &RPPXQ )URVW $$ 0XVXOLQ % &KHP 3K\V -DKQ +$ 7HOOHU ( 3URF 5R\ 6RF $ 3HLHUOV 5( ,Q 4XDQWXP 7KHRU\ RI 6ROLGV 2[IRUG 8QLY 3UHVV /RQGRQ S :LOOLDPV -0 ,Q $GY OQRUJ &KHP 5DGLRFKHP Df 6KLUDNDZD + /RXLV (0DF'LDUPLG $* &KLDQJ &. +HHJHU $&KHP 6RF &KHP &RPPXQ Ef &KLDQJ &. 'UX\ 0$ *DX 6& +HHJHU $/RXLV (0DF'LDUPLG $* 3DUN <: 6KLUDNDZD + $P &KHP 6RF 6X :3 6FKULHIIHU -5 +HHJHU $3K\V 5HY /HWW 0DDUPDQ + 7KHRSKLORX 1 6\QWK 0HW +DQGERRN RI &RQGXFWLQJ 3RO\PHUVn 6NRWKHLP 7$ (OVHQEDXPHU 5/ 5H\QROGV -5 (GV 0DUFHO 'HNNHU 1HZ
PAGE 145

*UHP /HGLW]N\ 8OOULFK % /HLVLQJ $GY 0DWHU 2KPRUL < 8FKLGD 0 0XUR
PAGE 146

Df +DWDQDND < +L\DPD 7 2UJ &KHP Ef +DWDQDND < +L\DPD 7 2UJ &KHP Ff +DWDQDND < 0DWVXL +L\DPD 7 7HWUDKHGURQ /HWW Gf +DWDQDND < +L\DPD 7 $P &KHP 6RF Hf 5HYLHZ +DWDQDND < +L\DPD 7 6\QOHWW Df 6X]XNL $ $FF &KHP 5HV Ef 6X]XNL $ 3XUH $SSO &KHP Ff 0L\DXUD 1 6X]XNL $ 6\QWK 2UJ &KHP -SQ Gf 0L\DXUD 1 6X]XNL $ 6\QWK 2UJ &KHP -SQ Hf 6X]XNL $ 3XUH $SSO &KHP If 6X]XNL $ 3XUH $SSO &KHP Df +HFN 5) $P &KHP 6RF Ef 5HFHQW 5HYLHZ &ULVS *7 &KHP 6RF 5HY 6RQRJDVKLUD 7RKGD < +DJLKDUD 1 7HWUDKHGURQ /HWW *HQHUDO 5HYLHZV Df .RFKL -. 2UJDQRPHWDOOLF 0HFKDQLVPV DQG &DWDO\VLVn $FDGHPLF 1HZ
PAGE 147

Df 1RUHQ *. 6WLOOH -. 0DFURPRO 5HY Ef *DOH '0 $SSO 3RO\P 6FL Ff %DXJKPDQ 5+ %UGDV -/ &KDQFH 55 (OVHQEDXPHU 5, 6FKDFNOHWWH /: &KHUQ 5HY Gf -RQHV 0% .RYDFLF 3 ,Q &RPSUHKHQVLYH 3RO\PHU 6FLHQFH $JJDUZDO 6/ 5XVVR 6 (GV 3HUJDPPRQ 2[IRUG 6XSSO S Df %XUURXJKHV -+ %UDGOH\ ''& %URZQ $5 0DUNV 51 0DFND\ )ULHQG 5+ %XP 3/ +ROPHV $% 1DWXUH Ef
PAGE 148

Df :DOORZ 7 1RYDN % 0 $P &KHP 6RF Ef 5DX ,8 5HKDKQ 0 0DNURPRO &KHP 3K\V Ff 5DX ,8 5HKDKQ 0 3RO\PHU Ff 5DX ,8 5HKDKQ 0 $FWD 3RO\PHULFD 5XONHQV 5 6FKXO]H 0 :HJQHU 0DFURPRO 5DSLG &RPPXQ Df &KLOG $' 5H\QROGV -5 0DFURPROHFXOHV Ef .LP 6 -DFNLZ 5RELQVRQ ( 6FKDQ]H 6 5H\QROGV 5 %DXU 5XEQHU 0 ) %RLOV 0DFURPROHFXOHV %URGRZVNL +RUYDWK $ %DOODXII 0 5HKDKQ 0 0DFURPROHFXOHV Df %DODQGD 3% 3K' 'LVVHUWDWLRQ 8QLYHUVLW\ RI )ORULGD Ef %DODQGD 3% 5DPH\ 0% 5H\QROGV -5 0DFURPROHFXOHV %DXU .LP 6 %DODQGD 3 % 5H\QROGV 5 5XEQHU 0 ) $GY 0DWHU &KDQJ 6& %KDUDWKDQ +HOJHVRQ 5 :XGO )
PAGE 149

&]HUZLQVNL : 1XFNHU 1 )LQN 6\QWK 0HW Df 'DQLHOL 5 2VWRMD 5 7LHFFR 0 =DPERQL 5 7DOLDQL & &KHP 6RF &KHP &RPPXQ Ef 0LWVXKDUD 7 7DQDND 6 .DHUL\DPD 0DNURPRO &KHP Ff 7DQDN 6 .DHUL\DPD +LUDLGH 7 0DNURPRO &KHP 5DSLG &RPPXQ Gf 5XL] -3 &KLOG $' 1D\DN 0DU\QLFN '6 5H\QROGV -5 6\QWK 0HW Hf 5H\QROGV -5 5XL] -3 &KLOG $' 1D\DN 0DU\QLFN '6 0DFURPROHFXOHV 3HOWHU $ 0DXG -0 -HQNLQV 6DGHND & &ROHV 7HWUDKHGURQ /HWW %DR = :DLNLQ &
PAGE 150

Df 7DWHLVKL 0 1LVKLKDUD + $UDPDNL &KHP /HWW Ef .DKDWD 7 2RVDZD 7 -33DWHQW > @ &KHP $EVWU 6FKRSRY 9RGHQLFKDURYD 0 0DNURPRO &KHP $JUDZDO $. -HQHNKH 6$ &KHP 0DWHU Df 'LHFN +$ +HFN 5) 2UJDQRPHW &KHP Ef &DVVDU 2UJDQRPHW &KHP Ff 6RQRJDVKLUD 7RKGD < +DJLKDUD 1 7HWUDKHGURQ /HWW 2VDNDGD 6DNDWD 5
PAGE 151

Df 5DX ,8 5HKDKQ 0 $FWD 3RO\PHU Ef %URGRZVNL +RUYDWK $ %DOODXII 0 5HKDKQ 0 0DFURPROHFXOHV +XHQLJ 6 %DX 5 .HPPHU 0 0HL[QHU + 0HW]HQWKLQ 7 (XU-2UJ&KHP 6DUDI 7 3DN 6FL OQG5HV

PAGE 152

%,2*5$3+,&$/ 6.(7&+ 0LFKDHO %ULDQ 5DPH\ VRQ RI -DPHV %REE\ DQG -HZHOO 6XH 5DPH\ ZDV ERP RQ -XO\ LQ .LQJVSRUW 71 0LFKDHO DWWHQGHG 3RZHOO 9DOOH\ +LJK 6FKRRO LQ UXUDO %LJ 6WRQH *DS 9LUJLQLD ZKHUH KH JUDGXDWHG YDOHGLFWRULDQ RI D FODVV RI VWXGHQWV $IWHU DWWHQGLQJ D VPDOO OLEHUDO DUWV FROOHJH IRU WZR \HDUV 0LFKDHO WUDQVIHUUHG WR 9LUJLQLD 3RO\WHFKQLF DQG 6WDWH 8QLYHUVLW\ 9$ 7HFKf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

PAGE 153

, 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 3KLORVRSKn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nG/ 'DQLHO 5 7DOKDP I 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\ $QWKRQ\ % WWUHQQDQ $VVRFLDWH 3URIHVVRU RI 0DWHULDOV 6FLHQFH DQG (QJLQHHULQJ

PAGE 154

PL 81,9(56,7< 2) )/25,'$


77
interesting new class of polyelectrolyte. In general, such polymers should be yellow in
color and emit in the green region of the visible color spectrum. Due to the extensive
rigid-rod character of PPEs, special care will have to be taken with the resulting
materials to determine the effect different side chains on the second phenylene ring in the
repeat unit will have on the solubility of the initial neutral polymer and subsequently the
effect of bulky organic groups on the properties of the post-polymerization quatemized
polymer. If successful, this set of PPE polymers may provide polymers that emit in a
similar wavelength range as the poly(p-phenylene-co-thiophenes) [PPTs] discussed in
Chapter 3 and are more efficient emitters, which are capable of being cast as free
standing thin films.
^6^13 C6Hi3
Figure 4-5. Representative structures of synthetic modifications to poly(p-
phenyleneethynylene)s.


13
Blue emission is found in poly(/?-phenylene) (PPP),lb polyalkylfluorene,17
fluorinated polyquinoline,18 PPP-based ladder copolymers,14 and lower gap polymers
with interrupted conjugation.20 PPV gives emission in the yellow-green light region and
the emission color can be moved toward the red by substitution with electron-donating
groups such as alkoxy chains at the 2- and 5- positions on the phenyl ring.21 The very
electron rich heterocycle containing polyalkylthiophenes emit in the red region of the
spectrum.22 Table 1-1 lists the polymers mentioned above with their corresponding
emission peak in nanometers. It should be noted for exact LED configuration the
reference for each type of polymer should be referred to as the negative electrode and
transport layer material in solid state emitting devices can affect emission characteristics.
The references listed represent the initial pioneering studies done on each material in the
early 1990s.
Many variations and methods of device construction have been attempted over the
last decade with the above polymer types and others to improve device output.
Discussion of all the variations in LED construction will not be presented here due to the
focus of this research being aimed at the syntheses of new conjugated polymers. In
particular, a focused discussion of the palladium(O) catalyzed Suzuki, Stille, and
Sonagashira coupling reactions will be conducted.
Palladium(O) Coupling Reactions
An important component was added to the toolbox of the synthetic organic
chemist in the early 1970s, by the development of cross coupling reactions involving
metal catalysis of organometallic species. Equation 1-3 illustrates the simple principles
involved in a cross coupling reaction. R and R are typically sp2 hybridized carbon


90
very high extent of polymerization, while PPE-NEt2/OC9(20)[54] remained soluble.
The gel was fully dissolved by the addition of an excess of chloroform. Both reactions
were precipitated into acetone after 24 hours and the collected polymers were washed
thoroughly with hot ethanol, acetone, and acetonitrile.
PPE-NEt2/OC9(High)[53] became insoluble upon complete drying with light
heating under vacuum. Elemental analysis of PPE-NEt2/OC9(High) indicated 0.55%
iodine by weight present in the sample which with the assumption that there is one iodine
molecule per chain indicates a degree of polymerization of 34 (68 rings). A small
amount of the dried PPE-NEt2/OC9(20)[54] would dissolve in refluxing chloroform and
a crude H NMR was acquired for the soluble portion. The spectrum was consistent with
the proposed polymer structure, but endgroup analysis was not definitive due to the low
concentration of the NMR sample and the inherent fractionation of the material.
The ability of the chains to pack in well-dried solid form prevents re-solvation of
the polymer chains and renders the materials unusable. After the initial work on the
polymers above, it was decided to repeat the PPE-NEt2/OC9(20)[54] polymerization and
prevent the complete drying of the material. Work with PPE-NEt2/OC9(20)[54] was
chosen over PPE-NEt2/OC9(High)[53] to ensure the greatest chance of maintaining
solubility. With a degree of polymerization of 20, PPE-NEt2/OC9(20)[54] will have
attained its maximum optical absorption and emission and if solubility can be maintained
will provide a useful polymer. It was decided not to extend the length of the alkoxy chain
to help prevent chain packing, as such an increase in the organic nature of the polymer
would be detrimental to the desired water solubility of the cationic derivatives to be
produced after polymerization. The second synthesis of PPE-NEt2/OC9(20)[54]


BIOGRAPHICAL SKETCH
Michael Brian Ramey, son of James Bobby and Jewell Sue Ramey, was bom on
July 24, 1973 in Kingsport, TN. Michael attended Powell Valley High School in rural
Big Stone Gap, Virginia, where he graduated valedictorian of a class of 169 students.
After attending a small liberal arts college for two years, Michael transferred to Virginia
Polytechnic and State University (VA Tech) in 1993. At VA Tech, Michael was an active
member of Alpha Chi Sigma, a professional co-educational chemistry fraternity and
performed basic undergraduate work for Dr. Judy Riffle. Michael graduated summa cum
laude with a Bachelor of Science degree in chemistry in 1996. After spending the
summer performing research for Milliken and Company in Spartanburg, South Carolina,
Michael arrived in Gainesville during August 1996 to begin his endeavor to become a
professional chemist. During the course of graduate school, Michael joined the research
group of Dr. John Reynolds, married Jennifer Carol Shelton in 1997, and is awaiting the
arrival of his first child in September 2001. Michael is a participant in the Palace Knight
Program with the United States Air Force, which has provided institutional and salary
funding through the final two years of graduate school. Post graduation in May 2001, the
Ramey family will reside in Dayton, Ohio, as Michael becomes a member of the research
laboratories at Wright Patterson Air Force Base.
140


64
The next synthetic progression after confirmation that a base set of PPT-NE2
polymers had been created was to try the Suzuki coupling methodology as outlined in
Figure 3-9. Compound 23 was added dropwise to a stirred solution of DINEt,
PdCFidppf), and NaHC3 in a DMF / H2O solvent solution at 70 C. After 3 days, the
reaction was precipitated into MeOH, the crude polymer recovered by filtration, followed
by extraction with MeOH and acetone for 24 hours each, and finally collected by
extraction with chloroform (via Soxhlet extractor). The material, PPT-NEt2(Suz)[29],
was recovered in 50% yield.
Figure 3-9. Synthesis of PPT-NEt2[29] via Suzuki coupling polymerization.
Elemental analysis of the polymer (see Table 3-5) initially indicated a possible
high molecular weight polymer with only 0.09 % by weight iodine found in the sample,
however, GPC trials indicated very low molecular weight oligomeric species. UV-Vis
absorption data showed a peak Xmax = 452 nm, some ten nanometers higher in wavelength
than the well analyzed materials from the Stille polymerization (see Physical Properties


4
j
low density, fibrous, and has few defect sites. Polyacetylene is intractable due to its
extensive conjugation and rigid nature. Just as mechanical properties build up with
additional coupling of monomer to polymer chains, electronic properties of 7t-conjugated
polymers grow analogously. Hiickel Molecular Orbital Theory provides a qualitative
description of the behavior of n electrons of planar conjugated systems and can be used
to explain the electronic behavior of such systems. The overlap integrals (S¡j) for orbitals
perpendicular to one another are considered to be zero.
This method can be utilized to describe the aromaticity in benzene and can be
extended to linear conjugated systems by treating them as giant cyclic structures with
equally spaced carbons. Orbital energies are given by the expression
E = a + 2/3cos(-?J) J= 1,2, ...,7V (1-1)
TV + 1
where 7 is the orbital number, counting upward from the lowest-energy orbital 7=1, and
N is the number of carbon atoms (also the number of basis orbitals) in the chain. The
binding energy of an electron to the 2p orbital is related to the Coulomb integral a. The
resonance integral (3 is related to the energy of an electron in the field of two nuclei. The
maximum energy between the lowest and highest molecular orbitals is arbitrarily set at a
constant value of 4(3. Figure 1-2 shows the application of the Frosts circle4 mnemonic to
illustrate to energy levels for cyclobutadiene and benzene.
As the number of linearly combined atomic orbitals increase (corresponding to
larger ring size in the Frost circle), it becomes clear that the energy difference between
molecular orbitals becomes increasingly small. The energy to excite an electron from the
HOMO to LUMO level would be insignificant relative to the thermal energy of an


This dissertation is dedicated to James B. and Jewell Q. Ramey, and Ralph and Georgia
Qualls whose lifelong work, encouragement, and love have made the construction of this
dissertation possible.


di(methanesulfonyl)-,48 and di(trifluoromethanesulfonyl) benzenes49 in the presence of
excess zinc have afforded functionalized PPPs (Figure 2-le,f ).
22
Figure 2-1. Synthetic methods to poly(p-phenylene).
(e)
(f)
Suzuki Couplings
A major improvement in PPP synthesis came in 1989 when Rehahn and
coworkers applied the more reactive Suzuki coupling reaction methodology to the


31
The original polymerizations were conducted by Dr. Peter Balanda and focused
on the synthesis of PPP-NE2 These initial synthetic investigations used DBNEt,
Pd(OAc)2 as the catalyst, with DMF, THF, and acetone as solvents. Usable polymeric
materials were synthesized, with DMF polymerizations giving the highest molecular
weights by GPC. Several obstacles remained. Using Pd(OAc)2 as catalyst resulted in the
precipitation of black, metallic Pd into solution and contamination of the polymer.
Removal of this impurity often proved difficult, if not impossible, and some loss of the
polymer was inevitable.
or
o
o
X
I
Br
k2C03
HpO
Pd catalyst
70 C
M2 W
organic solvent
O
O
O
O
Figure 2-10. Suzuki polymerizations for neutral alkoxy-amine containing PPPs.


82
cleavage of the triethylamine side groups and attempted recrystallization led to both
impurities and the desired compound to crystallized from the chosen solvents.
Taking into account the limitations imposed to purification by the polar amine
side groups of DINEt, it was desirous to have an alternate di-iodo monomer that
possesses the ability to form cationic amine sites, but does not contain amine sites from
the initial compound synthesis A route found in the literature used bromo-terminated
alkyl groups as side chains on benzene that were treated with triethylamine, imparting
water solubility with the resulting quatemized amine functionalities.104 Figure 4-9
outlines the synthesis of 2,5-bis(6-bromohexyl)-l,4-diiodobenzene which provides an
optional monomer to DINEt. It should be noted that this monomer does not have alkoxy,
but rather alkyl side chains and upon incorporation into a polymer backbone would raise
the energy of the n to n* transition compared to alkoxy containing PPEs.
Isolation of intermediate 43 was a challenging step in that that the presence of
unreacted starting material 42, which will prevent isolation of compound 44 in later steps,
must be removed by careful spinning band distillation under reduced pressure. The
distillation technique and equipment are dependent on user ability and several trials had
to be performed in order to maximize the separation ability of the apparatus. A rather
large spinning band column was used as lOOg batches of compound 43 were typically
synthesized. Figure 4-10 shows the GC chromatogram of the reduced pressure
distillation of compound 43 using a simple vigreux column followed by a purification
using the spinning band technique. The initial simple distillation is not necessary for
purification, but was conducted to show the separation advantages of the spinning band
column. The small amount of 1,6-dimethoxyhexane present in the post- spinning band


CHAPTER 6
EXPERIMENTAL
Reagents and Solvents. All reagents and solvents were purchased from Aldrich
or Fisher unless otherwise noted. Pd catalysts were purchased exclusively from Strem
Chemical. 1,4-Dibromobenzene and 4,4-dibromobiphenyl (Aldrich) were recrystallized
from hot pentane and toluene. Tetrahydrofuran (THF), toluene, and diethyl ether used in
Grignard, alkyllithium, or polymerization reactions were distilled from Na/K allow.
Anhydrous DMF and diisopropylamine were purchased from Aldrich. The diboronic
esters, 8 and 9, were synthesized by in situ transesterification with neopentyl glycol of the
diboronic acids made by literature methods.63
General Methods. NMR spectra were obtained with a Varan VXR-300 or a
Varan Gemini-300. Elemental analyses were performed by Robertson Microlit, Inc. or
in house by combustion with a Fisons/Carlo-Erba 1106 and 1108. Ultraviolet-visible
(UV-Vis) spectra were recorded using a Varan Cary 5E UV-Vis-NIR spectrophotometer
with measurements taken as the average of three separate samples for the molar
absorptivies data presented for polymers. Fluorescence results were obtained with a Spex
F-l 12 photon counting fluorimeter at room temperature. TGA was performed under N2
with a Perkin-Elmer TGA 7 Thermogravimetric Analyzer at 10C per minute under N2
atmosphere. GPC results were obtained with a system consisting of a Waters Model 590
pump, two 300 x 7.5 mm Polymer Laboratories Linear Mixed Bed (Plgel 5pm mixed-C)
columns in series and using a Spectraflow 757 Tunable UV-Vis Detector. Gas
chromatography measurements were performed on a Shimadzu GC-17A utilizing a 15
107


89
polymer coating on the reaction vessel. When excited by a UV lamp, an intense yellow-
green emission was observed. Upon cooling, excess solvent was removed and the
remaining solution was precipitated into MeOH. Quantitative yield of a yellow-orange
material was recovered and extracted successively with MeOH, acetone, and CHCI3 via
Soxhlet extraction. Only 2% of the initially precipitated material dissolved after stirring
in boiling chloroform, toluene, or 1,2-dichlorobenzene. The fact that the polymer was
soluble during the polymerization and insoluble after precipitation, supports the
hypothesis that the hexyloxy chains are sufficiently long to make the polymer soluble in
toluene, but aggregation and packing ability are at such high levels for the solid,
precipitated PPE-NEt2/OC6[52] that the polymer chains can no longer be separated and
solvated by common organic solvents. Elemental analyses of the insoluble materials is
shown in Table 4-1.
In order to overcome the solubility problem, the longer nonyl-oxy side chain
reagent 40 was used in the Sonogashira polymerization. Two polymerizations were
performed using the same conditions as the above PPE polymers. One reaction was
conducted to produce the highest molecular weight polymer possible (PPE-
NEt2/OC9(High)[53]) and the other polymerization was conducted with the addition of a
small amount of iodobenzene to limit chain length (theoretically calculated to give a
degree of polymerization of 20 (40 rings) using simple step-growth polymerization
equations) to synthesize PPE-NEt;>/OC9(20)[54]. The addition of the endcapping reagent
should limit chain length to improve solubility and give definitive 'H NMR signals for
determination of number average molecular weights. During the coarse of
polymerization, PPE-NEt2/OC9(High)[53] formed a gel-like suspension, indicating a


108
meter long Restek Corporation RTX-5 crossbond 5% diphenyl-95% dimethylsiloxane
column. The heating profile used consisted of holding at 50C for 3 minutes, heating to
275 C at a rate of 10 C per minute, and holding at the final temperature for 2 minutes
prior to cooling.
Chapter 2
2.5-dimethoxy-l,4-diiodobenzene (5). A 250 mL, 3 neck round bottom flask
was charged with 1,4-dimethoxybenzene (4) (10.48 g, 75.85 mmol) and a solvent system
consisting of 90:7:3 HO Ac/ H2O/ H2S04by volume. The reaction mixture was stirred
under Ar until the 1,4-dimethoxybenzene dissolved completely. I2 (23.66 g, 91.02 mmol)
and KIO4 (20.93 g, 91.02 mmol) were added and the reaction heated to 70 C overnight.
The reaction was cooled, poured into 500 mL H20, and a crude orange solid collected.
The crude solid was recrystallized from THF/H2O yielding a light yellow solid (24.03 g,
81% yield), mp 168-170 C (lit. mp105 169 C) H NMR (300 MHz, CDC13) 7.20 (s, 2
H), 3.83 (s, 6 H) ppm. '3C NMR (75.5 MHz, CDCI3) 153.29, 121.57, 85.44, 57.17 ppm.
Anal. Caled for CgHgOzL: C, 24.62; H, 2.05. Found: C, 24.31; H, 1.89. EI-LRMS
calculated for CgHgC^L: 389.9, Found 390.
2.5-diiodohydroquinone (DIHQ). 2,5-dimethoxy-l,4-diiodobenzene (10.00 g,
25.60 mmol) was dissolved in 50 mL dichloromethane and cooled in a dry ice/acetone
bath. Boron tribromide (26.50 g, 105.80 mmol) in 15 mL dichloromethane was added
dropwise via an addition funnel to the solution with stirring. The reaction mixture was
held at -78 C for 30 min and then allowed to warm to room temperature overnight. The
reaction was added slowly to 300 mL of ice water. A brown precipitate was collected
and recrystallized from THF / H2O leaving a white crystalline material (7.05 g, 76%


94
Polymer Quatemization
Figure 4-17 outlines two routes to synthesizing cationic polyelectrolytes from
PPE-NEt2/OC9(20)[54], Direct treatment of the neutral polymer in EtOH with 1M HC1
to lower pH and protonate the amine sites was a successful methodology to create a
polyelectrolye, PPE-NEt2H+/OC9(20)[55] that was soluble in the lowered pH ethanol
and displayed interesting physical properties different from the neutral version (to be
discussed in Physical Properties section). Unfortunately, the PPE-NEt2H+/OC9(20)[55]
was not soluble in lowered pH water alone, but required the addition of ethanol or 2-
propanol to dissolve. Solutions of the neutral polymer in lowered pH ethanol were cast
onto Teflon and could be removed as free standing thin films. The solutions also have
the capability to be directly used in electrostatic deposition experiments and avoid the
added synthetic step of quatemization with bromoethane and its difficulties to be
described below.
Figure 4-17. Conversion of PPE-NEt2/OC9(20)[54] to cationic polyelectrolytes.


109
yield), mp 192-193 C (lit. mp.62 192 194 C). H NMR (300 MHz, acetone-d6) 8.75 (s,
2 H), 7.30 (s, 2 H) ppm. C NMR (75 MHz, acetone-^) 151.58, 124.93, 84.25 ppm.
Anal. Caled for C6H402I2: C, 19.90; H, 1.11. Found: C, 19.73; H, 1.08. EI-LRMS
calculated forC6H402I2: 361.8, Found 362.
2.5-Dibromohydroquinone (DBHQ). A 2 liter, 3 neck round bottom flask
equipped with magnetic stir bar, addition funnel, and nitrogen gas inlet and outlet tubing
was charged with 500 mL of glacial acetic acid and 500 mL of methylene chloride.
Hydroquinone (6) (30.00 g, 273.7 mmol) was added and remained undissolved. With
vigorous stirring, 2.1 eq. of Br2 (91.64 g, 572.2 mmol) was slowly added to the reaction
flask from the addition funnel. Upon addition of the first equivalent of Br2, the
monobrominated species became soluble in the acetic acid / methylene chloride system.
After the addition of 1 equivalent of Br2 was complete, the dibromated compound began
to precipitate from the solution as a pale pink solid. After total addition of the Br2, the
mixture was stirred for 3 hours. During the reaction, a slow stream of nitrogen was
passed over the reaction and vented to a bath of aqueous sodium hydroxide to neutralize
the HBr gas being liberated from the large scale reaction. The crude product was isolated
by filtration and purified by recrystallization from a 5:1 (v/v) ispropanol / water solution.
A white crystalline solid was recovered (29.34 g, 40% yield), mp 184-185 C (lit. mp.106
185 186 C). H NMR (300 MHz, DMSO-rf6) 9.81 (s, 2 H), 7.01 (s, 2 H) ppm.
2.5-bis(3-[W,A-diethylamino]-l-oxapropyl)-l,4-diiodobenzene (DINEt). A 3
neck round bottom flask was equipped with a reflux condenser and Ar gas inlet. 2,5-
diiodohydroquinone (6.45 g, 17.82 mmol), 2-chlorotriethylamine hydrochloride (7) (6.75
g, 39.21 mmol), and K2CC>3 (10.33 g, 74.85 mmol) were added to the reaction flask. 150


118
solid was recovered and recrystallized from hexane and a minimal amount of toluene
(6.19 g, 70% yield), mp 158 C (lit. mp.63 157-158 C) 'h NMR (300 MHz, CDC13)
7.57 (s, 2 H), 3.74 (s, 8 H), 1.00 (s, 12 H) ppm. 3C NMR (75 MHz, CDC13) 136.23,
72.34, 32.01, 21.90 ppm. Anal. Caled for C14H2204SB2: C, 54.52; H, 7.20. Found: C,
54.70; H, 7.14. FAB-HRMS (M )+ calculated for C14H2204SB2: 308.1425, Found
308.1393.
2,5-bis(tolyl)thiophene [Suzuki test reactions] (24). For all reactions,
compound 23 (0.10 g, 0.32 mmol), 4-bromotoluene (0.11 g, 0.65 mmol), NaHC3(0.27g,
3.25 mmol), and 1 mol% PdCl2(dppf) were used. Solvents were varied among THF,
DMF, and toluene in a 5:1 by volume ratio with H20. Reactions were conducted at room
temperature, 72 UC, or reflux either as one pot type reactions or compound 3 was added
slowly to the reaction. 25 mL of H20 and 50 mL of Et20 were added after 6 hours. The
organic layer was analyzed via gas chromatography and product identity determined
solely by mass spectroscopy (GC/MS). No further identification or purification of the
reactions was conducted. Table 3-1 summarizes the GC/MS results.
Poly({2,5-bis[2-(Ar,A-diethylamino)-l-oxapropyl]-l,4-phenylene}-a/f-2,5-
thienylene) (PPT-NEt2).
General Procedure for Stille One Pot Synthesis. A 20 mL Schlenk flask with
stir bar was charged with DINEt and 2,5-bis(trimethylstannyl)thiophene (21). The flask
was evacuated and backfilled with Ar three times. 20 mL of anhydrous DMF, previously
sparged with Ar for 30 min., was added to the reaction flask via syringe. The reaction
mixture was stirred and heated to 50 C, allowing all monomers to dissolve. PdCl2(PPh3)2
was added in one portion and the reaction heated at 70 C for a variable number of hours.


91
provided a polymer that maintained solubility to a reasonable level in chloroform (~10
mg/mL) after drying overnight in a steady stream of air. The polymer was bright yellow
in color indicating little crosslinking or diyne defects had occurred and was recovered in
high yield (98%).
Determination of the molecular weight of the rigid PPE-NEt2/OC9(20)[54] via
standard gel permeation chromatography (GPC) proved inconclusive. Although
sufficiently soluble in chloroform to perform the analysis, peaks detected by UV
absorption appeared only at the end of the column volume. The PPE polymer interacted
with and adsorbed to the column packing material in such a way as to prevent separation
by size. This is not an uncommon phenomenon, especially with polar polymers which
can possibly bind to the column material. The rigid nature of the polymers, excluding
column sticking effects, normally cause a decrease in the retention time of the sample
when compared to polystyrene standards of the approximate same molecular weight
further complicating molecular weight determination by this method.
H NMR, UV absorbance, and film casting were used to substantiate that the
material was polymeric. Free standing orange films of PPE-NEt2/OC9(20)[54] could be
cast from chloroform solutions onto glass or Teflon substrates. Figure 4-15 shows both
the 'id and ljC NMR for PPE-NEt2/OC9(20)[54] in CDCI3 which gave expected shift
values with the proton peaks appearing as broad multiplets with poor splitting. Figure 4-
16 shows an expansion of the aromatic region, along with integral values for the peaks in
order to calculate an approximate degree of polymerization for PPE-NEt2/OC9(20)[54],


105
of polymerization of 23 (46 rings). GPC determinations of polydispersity and molecular
weights were unsuccessful at this time due to polymer interactions with the column
packing material.
The neutral PPE type polymer, PPE-NEt2/OC9(20)[54], could be dissolved in
organic solvents and dramatically increased emission was observed when the polymer
was dissolved in ethanol of lowered pH, PPE-NEt2H+/OC9(20)[55]. The acidic solution
protonates the amine sites and prevents quenching of the fluorescence by the lone pair of
electrons on the free amine. Optical data have shown that the polymers emit in the blue-
green region of the visible spectrum in solution (464 nm) and the solution quantum yield
improves from 0.001 to 0.86 in the case of the neutral compared to the protonated
polymer. Thermal degradation of PPE-NEt2H+/OC9(20)[55] was initiated at 188 C
under N2 (loss of HC1) followed by a steady decline in weight (20% weight % left at 522
C). Complete degradation occurs by a temperature of 700 C. Treatment of the neutral
polymer with bromoethane promoted insolubility of the resulting partially quatemized
polymer and was thus ineffective in producing a useful polyelectrolyte.
Taking into account the discoveries and observations made over the coarse of the
graduate research, it becomes only natural to look at which facets of the research should
continue in order to produce the most impact for future endeavors. This dissertation
frames the synthetic protocols of a variety of Pd(0) polymerizations with the
methodologies explained in a manner that can only be gained from hands-on
experimentation. The insights should be invaluable to future students in the Reynolds
research group to construct conjugated polymers not even envisioned at this point. More
direct in nature, future work could extend the experimental procedures to construct a


33
increase in the reductive elimination step, which is often the rate limiting step in Suzuki
couplings, thus increasing the overall rate of the reaction.
Polymerizations of bisneopentylglycol-l,4-phenylenediboronate and DBNEt
with PdCl2(dppf) in THF / aq. NaHCC>3 at 75 C for 3 days yielded improvements over
previous work [PPP-NEt2(dppf)[12]] A polymer with higher molecular weight,
Mn=18,700 g/mol [compared to 15,900 g/mol for Pd(OAc)2 in DMF polymer PPP-
NEt2(Br-72)[14]], and lower polydispersity index of 1.18 was synthesized (see Table 2-
1). Elemental analysis for the polymers and other compounds discussed throughout this
chapter are shown in Table 2-2. Figure 2-12 shows the GPC trace for PPP-
NEt2(dppf)[12]. GPC traces for the other PPP-NEt2 polymers are similar with retention
time and peak width varying for molecular weight and polydispersity, respectively. Scale
up by a factor of 2 to 3 times the original scale was successful using the PdCECdppf)
catalyst as well as prevention of Pd(0) contamination. Data shown in Table 2-1 for the
Pd(OAc)2 polymers was taken from the dissertation of Dr. Peter Balanda. Subsequent
polymerizations conducted using Pd(OAc)2 reproduced this data within experimental
errors. It should be noted that the low polydispersity found for the PdCbidppf) is an
effect of the polymer isolation procedures, which in all likelihood fractionated off some
lower molecular weight species. Suzuki polymerizations should behave like traditional
condensation polymerizations with statistically governed polydispersities of 2.
It was further believed that the use of the more active iodinated species, DINEt,
would lead to an increase in molecular weight. Using identical protocols, reactions were
conducted to couple DINEt or DBNEt with bisneopentylglycol-l,4-phenylene
diboronate (8) via Suzuki protocol. Both reactions were quenched by precipitation into


6
electrons, the energy of these orbitals change as a consequence of a symmetry lowering
vibration. The orbitals become nondegenerate and the total energy of the system is
lowered.
In solid state physics terminology, the Jahn-Teller effect is known as a Peierls
distortion0 and opens a gap in the pz band which physically distorts the polymer chain to
achieve a lower energy. Figure 1-3 graphically represents the effect of the Peierls
distortion on the band structure and density of states (DOS) of polyacetylene. Figure 1-
3a,b would exemplify a metallic conductor with no energy difference for electrons to
migrate into the unfilled conduction band. Figure l-3c,d demonstrates that as adjacent
carbons along the polymer chain dimerize, alternate single and double bonds are formed
as a discrete energy/band gap develops (Eg). The pz band is broken into an empty
conduction and a full valence band. Polyacetylene is a semiconductor (a < 10'5 S cm'1)
with a band-gap (Eg) of 1.4 eV.7
Polyacetylene can reach conductivities on the order of 104 S cm'1 by the addition
of electrons into the conduction band or removal of electrons from the valence band,
o
termed n-doping and p-doping, respectively. These processes result in further structural
changes in the system and defects known as solitons are formed.9 A negative soliton
corresponds to a resonance stabilized carbanion and a positive soliton corresponds to a
resonance stabilized carbocation. These charged solitons move under the influence of an
applied electric field.10
From the initial discoveries concerning the conductive and redox chemistry of
polyacetylene, the field of electroactive polymers has exploded into one of the most


polyelectrolyte. Significant changes in the polymers visible absorption and emission
)
wavelengths occur between the differing backbone structures. The polyelectrolytes
optical transitions are shifted to higher energies (blue-shifted) versus the absorption and
emission of the neutral version within the same polymer backbone type.
The effects of halogenation of the monomer, solvent type, and palladium catalyst
on the molecular weight were determined for each set of neutral polymers by monitoring
chain extension by gel permeation chromatography. In the case of the PPP derivatives, it
was found that the Suzuki polymerization proceeds the fastest to maximum molecular
weight in a DMF / aqueous media using PdCl2(dppf) catalyst with di-iodinated
monomer. Polymerizations using di-brominated monomers reached similar molecular
weight values but only after longer reaction times. Polymer chain growth in this system
was limited by the precipitation of polymer from the reaction solution and not the
reactivity of the halogenated monomer. PPT polymers synthesized using the Stille
reaction proceeded to highest molecular weight values in anhydrous DMF using
PdCl2(PPh3)2 catalyst and di-iodinated monomer. Triethylamine / THF solvent systems
using PdCl2(PPh3)2 catalyst with a small amount of Cul co-catalyst and di-iodinated
monomer were the best conditions for the PPE Sonagashira polymerizations. Di-
brominated monomers were ineffective in reaching polymeric materials when used in
either Stille or Sonagashira polymerizations. The conversion procedure to the
polyelectrolyte was determined to be sufficiently mild not to induce breakages of the
backbone, thus allowing the molecular weight characteristics for the neutral species to be
roughly applied to the polyelectrolyte.
Xll


115
washed with methanol then water, dried in an air stream, then dried in vacuo at 60C
overnight. Yield: 0.2990 g [51 %]. Anal, caled for C30H38N2O2: C, 78.60; H, 8.30; N,
6.11. Found: C, 70.25; H, 8.22; N, 5.75; Br, 1.21. NMR (300 MHz, CDCI3) 7.72
(bm, 8 H), 7.10 (bm. 2 H), 4.10 (bm, 4 H), 2.83 (bm, 4 H), 2.55 (bm, 8 H), 1.00 (bm, 12
H) ppm. 13c NMR (75.5 MHz, CDCI3) 150.39, 137.58, 130.00, 126.66, 116.20, 68.38,
51.85, 47.76, 11.89 ppm. GPC (CHCI3 vs. PS) Mn = 3,400 gmol'1, MP = 5,300 gmol'1,
Mw = 8,900 gmol'1, Mw/Mn = 2.6 (GPC curve shape poor). UV-Vis (THF) ^max = 350
nm, log ^max = 3.98; Amax = 290 nm, log £max = 3.70. PL (THF with 370 nm excitation)
^max 435 nm.
Quaternization of Polymeric Amino-Functionalized Poly(p-Phenylene)s.
Synthesis, percent yields, NMR, and optical transitions for all cationic PPP-NEt3+
samples were nearly identical, therefore, experimental details and characterization data
are listed only for the quaternization of PPP-NE2 (dppf)[12] to the cationic, water
soluble polymer.
Poly{2,5-bis[2-(A^A,A-triethylammonium)-l-oxapropyl]-l,4-phenylene-tf/f-
1,4 phenylene} dibromide [PPP-NEt3+[19]]. A 250 mL single neck round bottom flask
with a magnetic spin bar was charged with PPP-NE2 (dppf)[12] (1.32 g, 3.46 mmol)
and stirred at room temperature with bromoethane (5 mL) in THF (20 mL) in a sealed
flask. The partially quatemized amine polymer PPP-NEt3+[19] precipitated out of
solution over the course of 5 days. The reaction was poured into acetone and a tan
polymer collected on a medium porosity glass frit. Yield: 1.72 [83%]. ]H NMR results.
*H NMR (300 MHz, D20) 7.9-.5 (bm, 6 H), 4.5-3.8 (bm, 4 H), 3.8-2.5 (bm, 16 H), 1.5-


57
PdCI2dppf
NaHC03
solvent, temp.,
method
24
Figure 3-6. Test coupling reaction of 2,5-thiophene diboronate ester and 4-bromotoluene.
Test reactions were monitored by thin layer chromatography to check for the
consumption of molecule 23 and 4-bromotoluene along with the appearance of new
compound spots. Reactions which displayed positive TLC results were worked up
isolating the organic products. Subsequently, the material was analyzed by gas
chromatography/mass spectrometry (GC/MS) to determine composition. Table 3-3 lists
the various reaction combinations and results.
Surprisingly, coupling to any significant level does not occur in THF. Typically,
even if THF proves to be a poor solvent for a Suzuki coupling, the reaction will proceed
to the 20-30% range. GC/MS peaks were assignable only to the starting materials with a
very small percent (<2%) of mono-substituted thiophene present upon slow addition of
the boronate ester. It was hypothesized that THF may be degrading the reactive thiophene
boronate ester. To help determine if this was the case, a small sample of compound 23
was placed in THF with catalyst and THF or DMF (and the correct ratio of water)
without 4-bromotoluene and heated to 50 C for 3 hours. The reactions were stopped
and analyzed by GC/MS. Both revealed the peak assignable to compound 23 with no
degradation products evident. From these results, it is evident that THF and DMF do not
have any degradation effects on the boronate ester. The use of toluene as a higher boiling
solvent did not promote the reaction and GC/MS revealed higher levels of degradation


67
The excitation wavelength corresponded to the Xmax of each polymers absorbance. The
spectra display the typical characteristics of conjugated polymers in solution with a
Stokes shifted emission maximum and tailing broadly to higher wavelengths. Table 3-6
summarizes the optical properties for both the neutral and water soluble PPT polymers.
Wavelength (nm)
Figure 3-11. Normalized UV-Vis absorption and solution photoluminescence for PPT-
NEt type polymers.
a) PPT-NEt3+[31] UV-Vis absorption in FEO.
b) PPT-NEt2[28] UV-Vis absorption in THF.
c) PPT-NEt3+[31] emission in FEO.
d) PPT-NEt2[28] emission in THF.
It is interesting to note that the trend of increased absorbance and emission
intensity when moving from neutral to quatemized species for the PPP-NE2 system was


56
that may deter the reaction. Figure 3-6 shows the general Suzuki coupling reaction
employed to check reaction parameters. A variety of conditions were used to couple
compound 23 and 4-bromotoluene. 4-bromotoluene was chosen over 4-iodotoluene
because of its lowered reactivity. In essence, if conditions are found to allow the
coupling to occur with bromo-reagents, iodo-reagents should perform better under the
same conditions and oftentimes the reactivity of bromo-compounds is sufficient for use in
Suzuki couplings eliminating the need for the more expensive iodine compounds.
Sodium bicarbonate (NaHC03) and PdCbdppf) (1 mol%) were used as base and
catalyst, respectively, in all test reactions. Solvents were varied between THF, DMF, and
toluene, along with adjusting the reaction temperature from reflux to room temperature.
In all cases a mixed 5:1 ratio of the organic solvent to water was used to promote
formation of the more reactive boronate anion. To account for the high reactivity the
thiophene diboronate ester, reactions were conducted via one pot or the diboronate ester
was added slowly in a solution of solvent from an addition funnel.
Br 2 2 eq- MF BrMg
S.
MgBr
B(OCH3)3 ho
OH
B.
\
THF
OH
22
40%
2
23
70%
Figure 3-5. Synthesis of 2,5-thiophene diboronate ester.


CHAPTER 2
CATIONIC POLY(/?-PHEN YLENE) S
Introduction
Early Synthetic Attempts
Poly(p-phenylene) (PPP) has long been a synthetic target for polymer chemists
IT
due to theoretical calculations and observations on ill-defined materials that show PPP
to possess good mechanical strength and high chemical resistivity.38 Possibly, the most
important property of PPP is its ability to be used as a blue emitter in electroluminescent
devices.39 The advantages of using a polymer to emit light in the consumer electronics
industry are immense, as the more numerous polymer processing techniques allow for the
creation of flat panel computer and high definition television screens unavailable with
traditional materials and techniques. A thin film of PPP is placed between a high work
function anode (indium tin oxide coated glass) and a low work function cathode
(calcium). Under appropriate forward bias, holes and electrons are injected into the
polymer film, resulting in the formation of positive polarons on one side of the film and
negative polarons on the opposite side. The polarons migrate toward each other and a
singlet exiton is formed resulting in the emission of blue light.
Two major factors have hindered the synthesis of PPP. As the number of rings in
an unsubstituted, linear "pure PPP" type polymer increase, solubility of the resulting
chain diminishes quickly, leading to an insoluble, intractable polymer that is of little or
no use. However, the methodology applied to solubilizing PPP can result in materials
20


66
Bromoethane
THF
RT/5d
PPT-NEt2 PPT-NEt3+
Figure 3-10. Quatemization of PPT-NEt2 to form PPT-NEt3+.
Physical Properties of PPT Type Polymers
Figure 3-11 shows the UV-Vis absorbance and photoluminescence spectra for
PPT-NEt2[28] in THF and PPT-NEt3+[31] in H2O (normalized for convenience). It is
interesting to note the dramatic shift in absorbance maximum between the neutral and
charged polymers. PPT-NEt2[28] exhibits a Xmax at 460 nm with a corresponding molar
absorptivity of about 18,000 L mol''em'1, while PPT-NEt3+[31]s Amax is blue shifted 49
nm to 411 nm with a corresponding molar absorptivity of about 16,000 L mol''em'1. The
blue shift of the n to 71* transition for these polymers may be due to a solvatochromic
effect. Fine tuning of the Xmax could be achieved by controlling the extent of
quatemization, as incomplete quatemization leads to a lower extent of hypsochromic
shift.
Solution photoluminescence experiments revealed peak emission wavelengths of
519 nm and 494 nm for PPT-NEt2[28] in THF and PPT-NEt3+[31] in H20, respectively.


28
Figure 2-8 outlines the preparation of various boronic reagents to be used in
conjunction with DBNEt and DINEt in the Suzuki polymerizations to follow. The
general reaction for all boronic species proceeds via the formation of the di-Grignard
reagent of dibromo-benzene or dibromo-biphenyl,63,64 followed by quenching with
trimethyl borate. The boronate intermediate can be treated with aqueous acid to form the
diboronic acid or with neopentyl glycol in a transesterification manner to produce the
diboronic ester. Drying of the hydroscopic boronic acid is troublesome, and with the
exact mass balance requirements necessary for polymerizations, the easily stored and
purified boronic ester was preferred. The reactions are carried out in one pot with overall
yields ranging from 30-40 %. Isolating the boronic acid, followed by transesterification
using benzene to azeotropically distill off the H2O by-product did not improve yields
substantially (5% gain).
X Product %Yield
I DINEt 75
Br DBNEt 38
Figure 2-7. Williamson etherification of DIHQ or DBHQ.


99
Conclusions
An interesting cationic poly(/?-phenyleneethynylene) (PPE-
NEt2H+/OC9(20)[55]) has been synthesized by application of the Heck-Cassar-
Sonogashira-Hagihara reaction. Using this reaction, very high molecular weight species
can be synthesized, aided by the precipitation of amine salts, which drive the
polymerization to completion. With the high rigidity and solubility issues of these PPE
systems, oftentimes it is more fruitful to limit molecular weight with endcapping agents
to improve solubility and aid in molecular weight determination via 'H NMR analysis.
The use of Pd(PPh3)4 as catalyst helps avoid stoichiometric imbalance problems that can
occur with monomer equivalencies when Pd(II) catalysts are used, but special care must
be taken in the handling of the air sensitive catalyst.
Using the conditions described in this chapter and the experimental section in
Chapter 5, the neutral polymer PPE-NEt2/OC9(20)[54] was isolated in nearly
quantitative yield, with special care taken to ensure the polymer chains did not aggregate
and decrease solubility post-precipitation. A number average molecular weight of 16,500
g/mol was estimated by H NMR, corresponding to a degree of polymerization of 23.
GPC determinations of polydispersity and molecular weights were unsuccessful at this
time due to several factors. Optical data have shown that the polymers emit in the blue-
green region of the visible spectrum in solution and the solution quantum yield improves
from 0.001 to 0.86 in the case of the neutral compared to the protonated polymer.
These results have open the door for continued research in PPE polymers for the
Reynolds research group. Using the experimental protocols outlined in this chapter,
future workers can further modify the PPE backbone structures to improve solubility


120
PPT-NEt2(240)[27]. Reaction time of 240 hours. Reagents: DINEt (1.4298 g,
2.552 mmol), 2,5-bis(trimethylstannyl)thiophene (21) (1.0456 g, 2.552 mmol), and 35 mg
of PdCl2(PPh3)2 (0.05 mmol). 0.81 g of polymer was recovered (82% yield). Anal, caled
for C22H32N202SIo.o37: C, 67.13; H, 8.14; N, 7.12; I, 1.19. Found: C, 63.99; H, 7.99; N,
6.51; I, 1.22. GPC (THF vs. PS) Mn = 4,200 g mol'1, MP = 5,400 g mol'1, M = 7,200
g mol'1, MjM = 1.71.
Procedure for Stille Drop wise Synthesis. PPT-NEt2 (96-drop)[28]. A 20 mL
Schlenk flask with stir bar was charged with DINEt (1.01 g, 1.80 mmol), 25 mg of
PdCl2(PPh3)2 (0.04 mmol), and 20 mL of anhydrous DMF, previously sparged with Ar
for 30 min. The solution was warmed to 70 C. 2,5-bis(trimethylstannyl)thiophene (21)
(0.74 g, 1.80 mmol) was dissolved in 15 mL of DMF and added to a 20 mL addition
funnel attached to the Schlenk flask. Compound 21 was added dropwise over the course
of 4 hours. The reaction mixture was held at 70 C for 96 hours. The DMF solution was
concentrated to ~5 mL and precipitated into 150 mL MeOH. A dark red solid was
collected on a medium porosity glass frit and subsequently extracted with MeOH for 24
hours, acetone for 24 hours, and then collected by extraction with chloroform (via
Soxhlet extraction). The chloroform soluble fraction was collected by evaporation of the
solvent and dried in vacuo at 50 C overnight. 0.59 g of polymer was recovered (84%
yield). H NMR (300 MHz, CDC13) 7.63 (bm, 2 H), 7.34 (bm. 2 H), 4.24 (bm, 4 H), 3.04
(bm, 4 H), 2.69 (bm, 8 H), 1.11 (bm, 12 H) ppm. 3C NMR (75 MHz, CDC13) 149.53,
139.09, 126.49, 123.26, 113.26, 68.36, 52.09, 42.88, 12.01 ppm. Anal, caled for
C22H32N202SIoo30:C, 67.38; H, 8.17; N, 7.15; 1,0.97. Found: C, 63.99; H, 8.02; N,


117
H), 0.38 (s, 18 H) ppm. '3C NMR (75 MHz, CDC13) 143.00, 135.80, -8.15 ppm. Anal.
Caled for C10H20SSn2: C, 29.32; H, 4.92. Found: C, 29.65; H, 4.60. FAB-HRMS (M +
H)+calculated for C10H21SSn2: 411.9330, Found 411.9494.
Thiophen-2,5-diyIdiboronic acid (22). Magnesium (3.14 g, 129.16 mmol) was
added to a 3 neck round bottom flask with reflux condenser and addition funned, llame
dried under vacuum, and backfilled with Ar. 100 mL of dry THF was added to the flask.
2.5-dibromothiophene (14.88 g, 61.50 mmol) was dissolved in 50 mL of THF and added
to the addition funnel. The dibromo solution was added slowly with stirring to the
magnesium and brought to reflux for 5 hours after the addition was complete. The
reaction was then cooled and chilled to -78 C. Trimethyl borate (13.42 g, 129.16 mmol)
was added dropwise to the Grignard reagent and allowed to warm to RT overnight. Et20
was added (200 mL) and 1M HC1 was added slowly to dissolve the Mg salts. The ether
layer was collected and the aqueous layer extracted with ether (3 x 100 mL). The
combined organics were evaporated leaving a smelly brown oil. The oil was successfully
precipitated into 1M HC1 and a solid collected. The solid was recrystallized from H20
and 3.93 g of a white material was collected. (40% yield). H NMR (300 MHz, DMSO-
d(,) 8.14 (s, 4 H), 7.65 (s, 2 H) ppm.
Bis-2,2-dimethyltrimethylene thiophen-2,5-diyldiboronate (23). Thiophene-
2.5-diyldiboronic acid (22) (4.69 g, 29.13 mmol), neopentylglycol (6.07 g, 58.26 mmol),
and 150 mL of benzene were added to a 250 mL round bottom flask equiped with a Dean
Stark trap and reflux condenser. The reaction was stirred and refluxed while the
H20/benzene azeotrope was collected in the trap. After 24 hours the reaction was cooled,
dried over MgS04, and the solvent removed by reduced pressure evaporation. A white


110
mL of acetone (dried over MgS04) was added and the reaction stirred and refluxed.
After 3 days, a yellow slurry was poured into 300 mL of H20 and a solid precipitate
collected. The filtrate was extracted with Et20 (300 mL x 1, 150 mL x 1, 50 mL x 1).
The solid precipitate was dissolved in Et20 and the organics combined. The combined
Et20 layers were washed with 1M NaOH (300 mL x 1, 150 mL x 1, 50 mL x 1), H20
(300 mL x 1), and brine (300 mL x 1). The Et20 layer was dried over MgS04 and the
solvent removed under reduced pressure leaving a yellowish white solid. The solid was
recrystallized twice from MeOH / H20 (7.49 g, 75% yield), mp 79-80 C. H NMR (300
MHz, CDC13) 7.21 (s, 2 H), 4.00 (t, J = 6.0 Hz, 4 H), 2.91 (t, J, = 6.0Hz, 4 H), 2.66 (q, J
= 7.2 Hz, 8 H), 1.08 (t, J = 7.2 Hz, 12 H) ppm. C NMR (75 MHz, CDC13) 152.84,
122.82, 86.02, 69.20, 51.49, 47.92, 12.09 ppm. Anal. Caled for C,8H3iN202I2: C, 38.59 ;
H, 5.40 ; N, 5.00; I, 45.30. Found: C, 38.81; H, 5.53; N, 4.90; I, 45.10. FAB-HRMS (M
+ H)+calculated for C,8H3iN202I2: 561.0475, Found 561.0492.
2,5-Bis(3-|7V,N-diethylamino]-l-oxapropyl)-l,4-dibromobenzene (DBNEt). A
500 mL round bottom flask with magnetic spin bar and reflux condenser was charged
with anhydrous potassium carbonate (72.0 g, 521 mmol), 2-chlorotriethylamine
hydrochloride (7) (22.56 g, 131 mmol), 2,5-dibromohydroquinone (DBHQ, 13.46 g, 50.2
mmol), and 300 mL acetone (dried over MgS04 previously). The reaction was brought
to reflux for three days. The reaction mixture was diluted with 300 mL water, dissolving
all salts. The product was extracted with ether (1 x 300, 2 x 200 mL) and the combined
organics washed with 1M NaOH (aq.) (2 x 100 mL), water (2 x 200 mL) and brine (1 x
200 mL). The solution was dried over MgS4, filtered and stripped of solvent by
vacuum evaporation to yield crude oily solids. The crude product was recrystallized from


21
that do not reflect the characteristics of "pure PPP". Thermal, mechanical, and chemical
stability are reduced and the optical absorption and emission wavelengths are shifted
from the expected values. Nevertheless, the molecular weight enhancements and
solubility of resulting substituted PPPs often outweigh the property differences between
themselves and pure PPP.
A second hindrance to PPP synthesis is that traditional polymerization techniques
are not designed to grow a chain via carbon-carbon bond formation, but typically via
carbon-heteroatom (oxygen or nitrogen) coupling. Often the somewhat exotic methods
used to create PPP actually enhance side reactions leading to structurally poor polymers.
Electrochemical polymerizations have been attempted both oxidatively with 1,4-
dialkoxybenzenes40 and reductively with 1,4-dihalobenzenes in the presence of a nickel
catalyst. Chemical oxidation polymerizations have been conducted with cupric chloride
(Figure 2-la).42 Thermal conversion of radically43 or transition metal polymerized44
protected 5,6-dihydroxy-1,3-cyclohexadiene to unsubstituted PPP overcame solubility
difficulties with soluble pre-polymer intermediates that can be processed and
subsequently converted to pure PPP (Figure 2-lb). Thermal cyclization of enediynes
and o-phenyldiynes gave PPPs and poly(l,4-naphthylenes), respectively (Figure 2-lc).43
Nickel catalyzed Grignard couplings of 1,4-dibromobenzene have also been performed
by Yamamoto et al. (Figure 2-Id).46 The Grignard coupling route provided structurally
pure PPP oligomers. This mild route was promising, but termination by inherent
chemistry or precipitation of the growing polymer negated higher molecular weights.
Attachment of alkyl side chains led to a more homogeneous polymerization and higher
degrees of polymerization. Nickel catalyzed homocoupling of dichloro-,47


83
distillation GC will not affect the next reaction and its presence is due to the fact that only
one major fraction was collected with priority on avoiding the higher boiling starting
material 42. Additional glassware pieces for the distillation apparatus have been
designed and allow for the collection of multiple fractions without disturbing the reduced
pressure of the column. Small changes in the pressure of the distillation during operation
will negate the separation benefits of the technique.
Br
42
NaOMe
MeOH / ether
reflux / 2 days
1. Mg
Br-0
Br Ni (0) cat.
Figure 4-9. Synthesis of 2,5-bis(6-bromohexyl)-l,4-diiodobenzene.
Pure compound 43 was reacted with Mg metal to form the Grignard reagent and is
added to a solution of 1,4-dibromobenzene and nickel catalyst to form compound 44,
which was isolated by simple vacuum distillation. The methoxy endroups were
converted to bromine by refluxing in a hydrogen bromide/acetic acid solution and
isolated as a colorless solid after recrystallization. This step was necessary as the
iodination conditions used to synthesize compound 46 were shown to cleave the methoxy
groups, giving a complex mixture of inseparable products. Compound 46 was collected


72
CuCu +
PPE oligomers
Br2
CHCI3
200 300 C
PPE
(b)
C'\
c,~7~
ci
Cl
fci
Cl
Cu electr. -1.7 V, 24 h
PPE (c)
0.1 M Bu4N+(CI04)
O O PPA
y /( + h2N NH2 h2so4
H2N NH2
(d)
Figure 4-1. Early synthetic methodologies toward poly(/?-phenyleneethynylene)s [PPE].
Palladium (0) Coupling Reactions
Due to the limitations of the above routes, palladium cross coupling of terminal
alkynes to aromatic bromides or iodides in amine solvents is often the preferred
methodology to synthesize well-defined and soluble PPEs. This procedure is called the


76
diisopropylamine/toluene mixture under PdChiPPh^VCuI catalysis led to polymers
without crosslinking and degrees of polymerization of up to 100. The same group
prepared interesting dialkoxy-substituted copolymers with 3-(dimethylamino)propyl and
7-carboxy-heptyl groups.94 Weder et al.95 utilized the branched solubilizing
ethylhexyloxy and linear octyloxy groups to prepare a polymer with a reported degree of
polymerization of 230, which were summarily reflected in the similar work of Swager
and coworkers who limited the molecular weight by the use of an imbalanced reaction
stoichiometry to ensure defined iodine endgroups.96
Other classes of PPEs have been created via the Sonogashira reaction that mix
di-alkoxy-substituted diiodides with different aromatic diynes. Examples include Wests
97
use of 1,4-diethynylbenzene (Figure 4-5a) and Swagers use of al,4-
no
diethynylpentiptycene monomer to provide bulky chain spacing side-groups (Figure 4-
5b) or a bisamide compound better film forming properties (Figure 4-5c).99 Aryl- and
alkyl-substituted PPEs, which resemble a true unsubstituted PPE the most, were first
reported in 1995 by Bunz and Mullen (Figure 4-5d).100 A complete coverage of all PPE
type polymers synthesized by Pd(0) coupling methodologies would be impossible in this
dissertation, however, two excellent reviews by Giesa and Bunz on the subject matter are
available for reference.101 Extensive work has also been accomplished in the field of
102
metal to ligand charge transfer between PPEs and coordinated metallic species.
The utility of the Sonogashira reaction for synthesizing well-defined PPEs, along
with its tolerance for functional groups, makes it applicable for incorporation of 2,5-
dialkoxyamine-phenylene units into a PPE backbone structure. These units can be
protonated with acidic treatment or quatemized with ethylbromide to provide an


135
38. (a) Noren, G.K.; Stille, J.K. Macromol. Rev. 1971, 5, 385. (b) Gale, D.M. J.
Appl. Polym. Sci. 1978, 22, 1971. (c) Baughman, R.H.; Brdas, J.L.; Chance,
R.R.; Elsenbaumer, R.I.; Schacklette, L.W. Chern. Rev. 1982, 82, 209. (d) Jones,
M.B.; Kovacic, P. In Comprehensive Polymer Science; Aggarwal, S.L., Russo, S.,
Eds.; Pergammon: Oxford, 1989; Suppl. 1, p. 318.
39. (a) Burroughes, J.H.; Bradley, D.D.C.; Brown, A.R.; Marks, R.N.; Mackay, K.;
Friend, R.H.; Bum, P.L.; Holmes, A.B. Nature 1990, 347, 539. (b) Yamamoto,
T. Prog. Poly. Sci. 1992, 17, 1153. (c) Grem, G.; Leditzky, G., Ullrich, B.;
Leising, G. Adv. Mater. 1992, 4, 36. (d) Stephens, E.B.; Tour, J.M.
Macromolecules 1993, 26, 2420.
40. Yamamoto, K.; Nishide, H.; Tsuchida, E. Polym. Bull. 1987, 17, 163.
41. Stille, J.K.; Gillimas, Y. Macromolecules 1971,4,515.
42. (a) Kovacic, P.; Wu, C. J. Poly. Sci. 1960, 47, 448. (b) Brown, C.E.; Kovacic,
P.; Wilkie, C.A.; Kinsinger, J.A.; Hein, R.E.; Yaniger, S.I.; Cody, R.B. J. Polym.
Sci., Polym. Chem. Ed. 1986, 24, 255.
43. Ballard, D.G.H.; Courtis, A.; Shirley, I.M.; Taylor, S.C. Macromolecules 1988,
21, 294.
44. Gin, D.L.; Conticello, V.P.; Grubbs, R.H. J. Am. Chem. Soc. 1992,114, 3167.
45. John, J.A.; Tour, J.M. J. Am. Chem. Soc. 1994, 116, 5011.
46. Yamamoto, T.; Hayashi, Y.; Yamamoto, Y. Bull. Chem. Soc. Jpn. 1978, 51,
2091.
47. (a) Wang, Y.; Quirk, R.P. Macromolecules 1995 28, 3495. (b) Kaeriyama, K.;
Mehta, M.A.; Masuda, H. Synth. Met. 1995, 507.
48. Percec, V.; Bae, J.-Y.; Zhao, M.; Hill, D. H. Macromolecules 1995, 28, 6726.
49. Percec, V.; Okita, S.; Weiss, R. Macromolecules 1992, 25, 1816.
50. Rehahn, M.; Schlter, A.-D.; Wegner, G.; Feast, W.J. Polymer 1989, 30, 1054.
51. Rehahn, M.; Schlter, A.-D.; Wegner, G.; Feast, W.J. Polymer 1989, 30, 1060.
52. Rehahn, M.; Schlter, A.-D.; Wegner, G.; Feast, W.J. Makromol. Chem 1990,
191, 1991.
53. (a) Lee, C.C.; Chu, S.-G.; Berry, G.C. J. Polym. Sci.: Polym. Phys. Ed. 1983,
21, 1573. (b) Metzger Cotts, P.; Berry, G.C. J. Polym. Sci.: Polym. Phys. Ed.
1983,27,1255.


126
12.5 mmol), PdCl2(PPh3)2 (0.06 g, 0.1 mmol), and Cul (0.016 g, 0.1 mmol). Product was
collected as a crude red solid and purified by column chromatography on silica gel
(toluene) followed by recrystallization from ethanol giving faint yellow crystals (1.71 g,
74% yield). H NMR (300 MHz, CDC13) 6.89 (s, 2 H), 3.94 (t, 4 H), 1.78 (m, 4 H),
1.50-1.27 (m, 24 H), 0.88 (t, 6 H), 0.25 (s, 18 H) ppm. '3C NMR (75 MHz, CDC13)
153.96, 117.11, 113.87, 101.02, 100.05, 69.39, 31.91, 29.61, 29.51, 29.45, 29.32, 26.03,
22.68, 14.13, -0.03 ppm. Anal. Caled for C34H58O2S2: C, 73.59 ; H, 10.54. Found: C,
73.76; H, 11.17. FAB-HRMS (M)+ calculated for 554.3975, Found
554.3978.
General Procedure for the removal of trimethylsilyl groups. The appropriate
1.4-bis((trimethysilyl)ethynyl)-2,5-dialkoxybenzene was dissolved in THF and excess
tetrabutylammonium fluoride was added with stirring. The solutions were stirred for two
hours during which time a very dark black coloration of the solution occurred. The
reaction was poured into 300 mL of H20 and extracted three times with hexanes. The
combined organics were washed with water and dried over MgSC>4. The solvent was
removed under reduced pressure and the solid products were recrystallized in hexane.
1.4-diethynylbenzene was further purified via vacuum sublimation.
1,4-diethynylbenzene (41). Reagents: l,4-bis((trimethysilyl)ethynyl)-benzene
(3.02 g, 11.2 mmol). Solid product was recrystallized from MeOH and vacuum sublimed
to produce 1.24 g of a white solid in 88% yield. H NMR (300 MHz, CDC13) 7.42 (s, 4
H), 3.15 (s, 2 H) ppm. '"c NMR (75 MHz, CDC13) 131.98, 122.57, 83.01, 79.03 ppm.
Anal. Caled for C10H6: C, 95.20 ; H, 4.80. Found: C, 95.60; H, 4.60. FAB-HRMS (M)+
calculated for CiqH6: 126.0470, Found 126.0475.


121
6.51; I, 0.98. GPC (THF vs. PS) Mn = 5,300 g mol'1, MP = 6,900 g mol1, Mw = 9,000
g mol"1, MjMn =1.70.
Procedure for Suzuki Dropwise Synthesis. PPT-NEti (Suz)[29]. A 50 mL
Schlenk flask with stir bar was charged with DINEt (0.8089 g, 1.44 mmol), 21 mg of
PdChidppf) (0.03 mmol), and NaHC03 (1.53 g, 14.43 mmol). 10 mL DMF and 5 mL of
H2O previously sparged with Ar for 30 min. were then added. The solution was warmed
to 70 C. Compound 23 (0.4449 g, 1.44 mmol) was dissolved in 10 mL of DMF and
added to a 20 mL addition funnel attached to the Schlenk flask. 23 was added dropwise
over the course of 4 hours. The reaction mixture was held at 70 C for 96 hours. The
solution was concentrated to ~5 mL and precipitated into 150 mL MeOH. A light red
solid was collected on a medium porosity glass frit and subsequently extracted with
MeOH for 24 hours, acetone for 24 hours, and then collected by extraction with
chloroform (via Soxhlet extraction). The chloroform soluble fraction was collected by
evaporation of the solvent and dried in vacuo at 50 C overnight. 0.28 g of polymer was
recovered (50% yield). H NMR (300 MHz, CDC13) 7.63 (bm, 2 H), 7.34 (bm. 2 H), 4.24
(bm, 4 H), 3.04 (bm, 4 H), 2.69 (bm, 8 H), 1.11 (bm, 12 H) ppm. Anal, caled for
C22H32N2O2S: C, 68.04; H, 8.23; N, 7.23. Found: C, 64.70; H, 7.98; N, 6.60; I, 0.09.
UV-Vis (THF) Xmax = 452 nm, log max = 3.98. GPC results showed a non-polymeric
distribution and very low molecular weight species.
General Quaternization Procedure. Neutral alkoxy-amine containing polymers
were stirred at room temperature with an excess of bromoethane in a minimal amount of
THF under Ar with stirring. The partially quatemized amine polymers began to
precipitate out of solution between 3-5 days at room temperature. The quatemized


70
Adjustment of the number of PPT-NEt3+[31] layers deposited and thickness of the
layers dramatically changes and allows fine tuning of the refractive index of the
transparent window created by the device.
Investigations of test reactions using Suzuki coupling techniques were successful
using a 2,5 thiophene diboronate ester, however, the reagent was too susceptible to
hydrolysis to allow the synthesis of high molecular weight polymers as evidenced by a
lower absorption wavelength maximum than the Stille polymers. The 2,5 thiophene
diboronate ester is a viable alternative to more hazardous and toxic 2,5-
bis(trialkylstannyl)thiophene reagents for Pd coupling reactions to di-substitute thiophene
in the 2,5 positions.


128
the reaction heated to 70 C overnight. The reaction was cooled, poured into 500 mL
H20, and extracted with chloroform (3 x 150). The combined organics were dried over
MgS04 and the solvent evaporated. Purification of the crude brown solid was
accomplished via recrystallization from MeOH and a minimal amount of acetone (2.20 g,
65% yield), mp 74-75 C. H NMR (300 MHz, CDC13) 7.59 (s, 2 H), 3.42 (t, 4 H), 2.61
(t, 4 H), 1.89 (m, 4 H), 1.42-1.57 (m, 12 H) ppm. '3C NMR (75 MHz, CDC13) 144.60,
139.32, 100.31, 39.64, 33.93, 32.67, 29.97, 28.38, 27.92 ppm. Anal. Caled for
C18H26Br2l2: C, 33.04 ; H, 4.01; I, 38.82. Found: C, 33.08; H, 3.98; I, 38.98. FAB-
HRMS (M)+calculated for C,8H26Br2I2: 653.8491, Found 653.8493.
2,5-Bis(6-phenoxyhexyl)-l,4-diiodobenzene (50). A solution of compound 46
(5.08 g, 7.77 mmol) in dry toluene (25 mL) was added slowly to a stirred solution of
phenol (2.82 g, 31.06 mmol), sodium r-butoxide (2.69 g, 27.18 mmol), and potassium
iodide (catalytic) in anhydrous DMF (75 mL). The mixture was stirred and refluxed for
16 hours. Water was added (100 mL) and the organic layer separated off with the
aqueous layer being extracted with benzene (3 x lOOmL). The combined organic layers
were washed with 1M NaOH (3 x lOOmL), water (2 x 100 mL), and brine (1 x 100 mL)
and dried over MgS04. The solvent was removed in vacuo and the obtained crude
product was recrystallized from hexane (3.91 g, 74% yield), mp. 88-89 C. H NMR (300
MHz, CDC13) 7.59 (s, 2 H), 7.26 (m, 4 H), 6.91 (m, 6 H), 3.96 (t, 4 H), 2.61 (t, 4 H), 1.81
(m, 4 H), 1.50 (m, 12 H) ppm. "c NMR (75 MHz, CDC13) 158.99, 144.65, 139.28,
129.37, 120.44, 114.43, 100.29, 67.69, 39.71, 30.11, 29.20, 29.03, 25.86 ppm. Anal.
Caled for C3oH3602I2: C, 52.78 ; H, 5.32. Found: C, 52.48; H, 5.69. FAB-HRMS (M)+
calculated for C3oH3602I2: 682.0805, Found 682.0766.


24
COOH
COOH
P
o
\
(CH2)6 r
'OaS
Figure 2-3. Anionic poly(p-phenylene)'s reported in the literature.
Highly charged cationic ammonium and pyridinium PPP polyelectrolytes were
reported in the mid 1990s by Rehahn and co-workers (Figure 2-4a,b).57 Dr. Peter B.
Balanda of the Reynolds research group used an alternate methodology to include
co
cationic quaternary ammonium salt side chains into a PPP backbone (Figure 2-4c).
Poly [2,5-bis(2- {N, N, A-triethylammonium} -1 -oxapropyl)-1,4-phenylene-a/t-1,4-
phenylene] dibromide (PPP-NEL+) was synthesized via a Suzuki protocol. The polymer
was used in the assembly of blue emitting solid state devices via layer-by-layer
polyelectrolyte self-assembly with sulfonatopropoxy PPP.59 The material also proved
very useful as a buffer layer for hybrid inkjet printed LEDs using sulfonatopropoxy
substituted poly(phenylene-vinylenes).60


41
Physical Properties of PPP Type Polymers
For optical display uses, such as organic light emitting devices (OLEDs)
envisioned for PPP-NEt3+[19], the two most important physical properties for the
polymer are absoiption and emission wavelengths and thermal stability. The absorption
and emission wavelengths will obviously control the color of the display device and
LEDs operating under a high bias are limited in lifetime by thermal and electric field
induced degradations. Materials with low barriers to thermal degradation are of limited
use.
The solution absorbance and emission behavior of the newest PPP-NEt2[12] and
PPP-NEt3+[19] samples match the data reported for the initial polymer samples prepared
by Dr. Peter Balanda. Absorption spectra for the neutral polymer in THF (plot c), neutral
polymer in 1M HC1 (plot b) and quatemized polymer in H2O (plot a) are represented on
the left half of the graph in Figure 2-16. Interestingly, a significant blue shifting of the
solution absoiption maximum occurs from the neutral (Xmax = 350 nm) to quatemized
(A.max = 330 nm) polymer. In theory, the charges formed on the amine sites along the
backbone of the PPP polymer should repel other polymer chains and each other on the
same chain, stiffening each chain. This new state of the polymer should reduce steric
interactions and red shift the absorbance to lower energy. If this red shifting is occurring,
it is overcome by the additional effect of creating very specific point charges in space
along the backbone which in turn have their own effect on the absorption pushing it into
higher energy levels.
The solution emission results are plotted on the right half of Figure 2-16 and are
shown on a log scale to allow a comparison of the large differences in intensity of


12
Table 1-1. Brief Summary of Emission Wavelength for Differing Conjugated Polymer
Structures.
along the backbone, addition of side-chain groups with electron donating or electron
withdrawing substituents, or disruption of conjugation length by insertion of non-
conjugated segments. The more electron rich a system is, the farther into the lower
energy, red emission portion of the visible spectrum it will be. Electron deficient
polymers will emit in the higher, blue emission portion of the spectrum.


CHAPTER 3
CATIONIC POLY(p-PHENYLENE-co-THIOPHENE)s
Introduction
While poly(p-phenylene)s such as PPP-NEt3+[19] are typically strong blue-
emitting polymers, it is desirable to have structurally similar materials with a range of
emission wavelengths. One approach to tune the emission wavelength of a polymer is
to chemically change the makeup of the backbone structure. By incorporation of more
electron rich moieties into the repeat unit structure, the highest occupied molecular
orbital (HOMO) to lowest occupied molecular orbital (LUMO) electronic bandgap is
lowered. Specifically, electron rich species raise the HOMO and have little effect on the
LUMO, thereby decreasing bandgap overall. As the bandgap is lowered, the energy
needed to excite an electron into the LUMO is reduced and therefore the energy
(wavelength) of light emitted upon relaxation will be of lower energy. For a more
complete description of light emission consult chapter 1 of this dissertation.
Inclusion of heterocycles, such as thiophene, furan, and pyrrole into co-polymers
with PPP attract much attention due to the substitution possibilities on phenylene rings
and the bandgap reduction due to a greater tendency towards planarity and electron
richness of the heterocycle. The original work to be discussed in this chapter will use the
incorporation of thiophene into the backbone of an alternating substituted phenylene-co
thiophene polymer to create a water soluble polymer that emits at higher wavelengths
than the parent PPP-NEt3+[19] polymer discussed in Chapter 2 of this dissertation.
47


37
Table 2-2. Elemental Analysis results for PPP monomers and polymers.
Species
%C
%H
%N
%l
%Br
Anal. Caled, for
Theo.
38.59
5.40
5.00
45.30
-
C18H30N2O2I2
DINEt
Exp.
38.81
5.53
4.90
-
-
Theo.
41.00
5.41
6.83
_
34.33
Ci4H22N202Br2
DBNEt
Exp.
41.13
5.44
6.71
-
-
Theo.
78.21
8.76
6.08
-
-
C30H40N2O2
PPPmodel
(10)
Exp.
78.41
9.56
5.90
-
-
PPPmodel+
Theo.
60.34
7.45
4.14
-
23.34
C34H5oN202Br2
(ID
Exp.
61.27
7.67
4.29
-
22.54
Theo
74.95
8.91
7.28
-
-
C24H34N2O2B10.026
PPP-NEt2
(dppf)[12]
Exp.
75.21
8.94
8.01
-
0.45
PPP-NEt2
Theo.
74.95
8.91
7.28
-
0.53
C24 H34N2O2BI0.026
(Br-72)[14]
Exp.
75.09
8.92
8.05
-
0.54
PPP-NEt2
Theo.
74.28
8.77
7.22
1.47
-
C24H34N2O2I0.O45
(I-3)[15]
Exp.
67.32
8.42
6.01
1.48
-
PPP-NEt2
Theo.
74.82
8.83
7.27
0.76
-
C24H34N2O2I0.O23
(I-24)[16]
Exp.
71.85
8.45
6.78
0.77
-
PPPBP-
Theo.
78.60
8.30
6.11
-
-
C30H38N2O2
NEt2[13]
Exp.
70.25
8.22
5.75
-
1.21
C24H34N2O2
PPP-NEt3+
Theo.
54.02
7.85
4.63
-
21.48
1.6 C2H5Br
[19]
Exp.
52.35
7.61
4.31
-
21.40
2.54 H20
PPPBP-
Theo.
60.27
7.09
8.05
-
23.63
C34H48N202Br2
NEt3+ [20]
Exp.
65.68
8.05
5.35
-
11.98


133
16. Grem, G.; Leditzky, G.; Ullrich, B.; Leising, G. Adv. Mater. 1992, 4, 36.
17. Ohmori, Y.; Uchida, M.; Muro, K.; Yoshino, K. Jpn. J. Appl. Phus. 1991, 30,
L1941.
18. Parker, I.D.; Pei, Q.; Marrocco, M. Appl. Phys. Lett. 1994, 65, 1272.
19. Grner, J.F.; Friend, R.H.; Scherf, U.; Huber, J.; Holmes, A.B. Adv. Mater.
1994, 6, 748.
20. (a) Bum, P.L.; Holmes, A.B.; Kraft, A.; Bradley, D.D.C.; Brown, A.R.; Friend,
R.H. J. Chem. Soc., Chem. Commun. 1992, 32. (b) Bum, P.L.; Holmes, A.B.;
Kraft, A.; Bradley, D.D.C.; Brown, A.R.; Friend, R.H.; Gymer, R.W. Nature
1992, 356, 47. (c) Braun, D.; Staring, E.G.J.; Demandt, R.C.J.E.; Rikken, L.J.;
Kessener, Y.A.R.R.; Venhuizen, A.H.J. Synth. Met. 1994, 6, 934. (d) Staring,
E.G.J.; Demandt, R.C.E.; Braun, D.; Rikken, G.L.J.; Kessener, Y.A.R.R.;
Venhuzen, T.H.J.; Wynberg, H.; ten Hoeve, W.; Spoelstra, K.J. Adv. Mater.
1994, 6, 934.
21. (a) Braun, D.; Heeger, A.J. Appl. Phys. Lett. 1991, 58, 1982. (b) Braun, D.;
Heeger, A.J. Appl. Phys. Lett. 1991, 59, 878.
22. (a) Ohmori, Y.; Uchida, M.; Muro, K.; Yoshino, K. Jpn. J. Appl. Phys. 1991,
30, L1938. (b) Braun, D.; Sutafson, G.; McBranch, D.; Heeger, A.J. J. Appl.
Phys. 1992, 72, 564. (c) Greenham, N. C.; Brown, A.R. Bradley, D.D.C.; Friend,
R.H. Synth. Met. 1993, 55-57, 4134.
23. Yamamura,M; Moritani, I.; Murahashi, S. J. Organomet. Chem. 1975, 91, C39.
24. (a) Negishi, E.; Baba, S. J. Chem. Soc., Chem. Commun. 1976, 596. (b) Baba,
S.; Negishi, E. J. Am. Chem. Soc. 1976, 98, 6729.
25. Negishi, E.; King, A.O.; Okukado, N. J. Org. Chem. 1977, 42, 1821.
26. Negishi, E.; Van Horn, D.E. J. Am. Chem. Soc. 1977, 99, 3168.
27. Murahashi, S;. Yamamura, M.; Yanagisawa, K.; Mita, N.; Kondo, K. J. Org.
Chem. 1979, 44, 2408.
28. (a) Milstein, D.; Stille, J.K. J. Am. Chem. Soc. 1979,101, 4992. (b) Scott, W.J.;
Crisp, G.T.; Stille, J.K. J. Am. Chem. Soc. 1984, 106, 4630. (c) Scott, W.J.;
Stille, J.K. J. Am. Chem. Soc. 1986, 108, 3033. (d) Echavarren, A.M.; Stille,
J.K. J. Am. Chem. Soc. 1987, 109, 5478. (e) Review: Stille, B.J. Angew. Chem.
lnt. Ed. Engl. 1986, 25, 508.


ACKNOWLEDGMENTS
The greatest acknowledgment goes to my Lord and Savior, Jesus Christ, whose
loving sacrifice wipes clean the imperfections of us all. My wife, Jennifer Ramey, has
walked hand in hand with me throughout my growth as a Christian and scientist and
without her support and love my life would not be complete. Family members mentioned
in the dedication essentially gave up a large portion of their lives in order to make mine a
success and that debt can never be repaid. The investment in my life was paid with the
sweat of their brow and with intellectual and emotional guidance. Now that I am
expecting the arrival of my first child in September 2001,1 can only hope to reflect the
same attitude to my son or daughter.
I would also like to thank those around me in the professional arena. Dr. John
Reynolds has helped guide me through the process of becoming a Ph.D. scientist and has
set an excellent example of the life of a Christian man. Dr. Kenneth Wagener has almost
been like a second research advisor to me as he is available and helpful for all students
who come to him in search of advice on research, professionalism, or life. The students,
post-docs, and visiting scientists make the George and Josephine Polymer Research
Laboratory an outstanding environment in which to work. Special thanks go out to my
closest friends on the polymer floor: Jason Smith and Cameron Church who have had the
pleasure of jumping through the same hoops and sharing the same experiences as
members of the same entering graduate class; Dean Welsh who is a fellow NASCAR
in


48
Early Synthetic Attempts
An early approach to incorporate thiophene units into a poly(p-phenylene-co-
thiophene) backbone was based on a poly( 1,4-diketone) prepared by a Stetter reaction
that was treated with Lawessons reagent to incorporate sulfur into the backbone (Figure
3-la).71 The harsh conditions required was a major flaw in this approach, as crosslinking
was promoted. Czerwinski et al. used a Grignard coupling between p-dibromobenzene
and 2,5-dibromothiophene in various feed ratios to incorporate thiophene and phenylene
units into the backbone (Figure 3-lb).72 Alternating copolymers containing arylene and
bithiophene repeat units have been synthesized via electrochemical polymerization of
l,4-di-2-thienylarylenes (Figure 3-lc).7 The electrochemical polymerizations form
insoluble films on conductive substrates limiting polymer processing to the initial
deposition. Pelter et al. used zinc chloride to metlate the 5 and 5 positions of l,4-di-(2-
thienyl)phenylene and reacted the intermediate with l,4-dibromo-2,5-disubstituted
benzenes via a Grignard coupling (Figure 3-ld).74 The polymers could be doped by
5 3 11
ferric chloride or iodine to conductivities between 10' and 10" D. cm' .
Dr. Fuping Yu and co-workers first report the synthesis of an alternating poly(/?-
phenylene-cothiophene) by a Stilie coupling polymerization in 199 3.75 The Stille
reaction offers much more flexibility in the selection of monomers and reaction
conditions than many of the pathways shown in Figure 3-1. Figure 3-2 shows a general
polymerization scheme for a Stille type polymerization. In this case, l,4-diiodo-2,5-
dialkoxybenzenes were reacted with 2,5-bis(tributylstannyl)thiophene. The polymers
were analyzed via gel permeation chromatography revealing a number average molecular


51
Table 3-1. Structures of the organohalides and triflates for the Stille reactions.
R
R
1-8
Compound
R
X
1
OC8H,7
I
2
oc8h17
Br
3
oc8h,7
OTf
4
C8H,7
I
5
C8H,7
Br
6
C8H,7
OTf
7
OC11H23
OTf
8
no substitution
OTf
*Taken from Bao, Z.; Waikin, C.; Yu, L. J. Am. Chem. Soc. 1995,117, 12426.
Table 3-2. Structures of the organotin monomers for the Stille reactions.
Compound
R
R
12
OCH3
CH3
13
OCH3
/1-C4H9
14
OC7H,5
CH3
*Taken from Bao, Z.; Waikin, C.;
Yu, L. J. Am. Chem. Soc.
1995, 117, 12426.
Typically 2 mol% catalyst was used as higher loadings of catalyst lowered
molecular weight. Adjustment of the 1:1 organohalide to organotin reactant equivalent


78
Results and Discussion
Monomer Syntheses
As illustrated in Figure 4-4, Sonogashira couplings require the usage of a di-
haloaromatic and a di-ethynylaromatic for an AA-BB type polymerization. Initial
monomer synthesis focused on the di-ethynyl reagent; the substitution of which will
greatly affect the solubility characteristics of the resulting polymer. Figure 4-6 outlines
the Williamson etherification procedure used to alkylate hydroquinone with
primary alkyl bromides.103 A suspension of powdered KOH was stirred in dry DMSO for
one hour followed by addition of hydroquinone and either hexyl- or nonyl-bromide. The
reactions were heated to 80 C for 12 hours, cooled, poured into ice water, and extracted
with hexanes. The organic layer was subsequently washed with 1M NaOH, water, brine,
Compound % Yield
32 83
33 79
Figure 4-6. Williamson etherification to synthesize various 1,4-dialkoxyphenylenes.
and dried over MgSCU. Removal of the solvent via reduced pressure evaporation led to
the isolation of reddish solids. The solids, l,4-bis(hexyloxy)benzene (32) and 1,4-
bis(nonyloxy)benzene (33), were purified by recrystallization from ethanol giving white
solids in 83 and 79 percent yields, respectively.


11
polymer repeat units. Calculations have shown that the triplet exciton is stabilized by
0.65 eV with respect to the singlet exciton and is localized over not much more than a
single polymer repeat unit for PPV.13 Figure 1-6 shows the relative arrangement of
ground and excited state energies for a conjugated polymer including the experimentally
measured higher energy triplet (T*). Typically, excitation occurs to a singlet exciton that
undergoes some vibrational release of energy and then returns to the ground state via the
release of light energy. The relaxation before emission of light results in the energy of
emitted light being of slightly lower energy than the energy of the n to n* level (Stokes
shift).
singlet
triplet
T
inter
system
crossing
absorption
induced absorption
luminescence
Figure 1-6. Electronic transitions in a conjugated polymer (i.e. PPV) showing both
singlet and triplet states.
Conjugated Polymers for Electroactive Applications
Control of the n to n* energy gap of a conjugated polymer is of utmost
importance in order to tune the wavelength of emitted light through the visible light
region. The energy gap can be modified by directly changing the type of conjugation


137
72. Czerwinski, W.; Nucker, N.; Fink, J. Synth. Met. 1988, 25, 71.
73. (a) Danieli, R.; Ostoja, R.; Tiecco, M.; Zamboni, R.; Taliani, C. J. Chem. Soc.,
Chem. Commun. 1986, 1473. (b) Mitsuhara, T.; Tanaka, S.; Kaeriyama, K.
Makromol. Chem. 1988, 189, 1755. (c) Tanak, S.; Kaeriyama, K.; Hiraide, T.
Makromol. Chem., Rapid Commun. 1988, 9, 743. (d) Ruiz, J.P.; Child, A.D.;
Nayak, K.; Marynick, D.S.; Reynolds, J.R. Synth. Met. 1991,47,783. (e)
Reynolds, J.R.; Ruiz, J.P.; Child, A.D.; Nayak, K.; Marynick, D.S.
Macromolecules. 1991, 24, 783.
74. Pelter, A.; Maud, J.M.; Jenkins, I.; Sadeka, C.; Coles, G. Tetrahedron Lett., 1989,
30, 3461.
75. Bao, Z.; Waikin, C.; Yu, L. Chem. Mater. 1993, 51, 2.
76. Bradley, D.D. Chem. Brit. 1991, 719.
77. Bao, Z.; Waikin, C.; Yu, L. J. Am. Chem. Soc. 1995, 117, 12426.
78. Farina, V.; Krishnan, B. J. Am. Chem. Soc. 1991, 113, 9585.
79. Echavarren, A.M.; Stille, J.K. J. Am. Chem. Soc. 1987, 109, 5478.
80. (a) Segelstein, B.E.; Butler, T.W.; Chenard, B.L. J. Org. Chem. 1995, 60, 12.
(b) Farina, V.; Krishnan, B.; Marshall, D.R.; Roth, G.P. J. Org. Chem. 1993, 58,
5434.
81. Seitz, D. E.; Lee, S-H.; Hanson, R. N.; Bottaro, J. C. Syn. Comm., 1983,13, 121.
82. Yang, J.S.; Swager, T.M. J. Am. Chem. Soc. 1998,120, 11864.
83. (a) Bumm, L.A.; Arnold, J.J.; Cygan, M.T.; Dunbar, T.D.; Burgin, T.P.; Jones, L.;
Aliara, D.L.; Tour, J.M.; Weiss, P.S. Science 1996, 277, 1705. (b)Samori,P;
Francke, V.; Mllen, K.; Rabe, J.P. Chem.Eur.J. 1999,5,2312. (c) Samori, P.;
Sikharulidze, I.; Francke, V.; Mllen, K.; Rabe, J.P. Nanotechnology 1999, 10,
77. (d) Samori, P; Francke, V.; Mllen, K.; Rabe, J.P. Thin Solid Films. 1998,
336, 13. (e) Samori, P; Francke, V.; Mangel, T.; Mllen, K.; Rabe, J.P. Opt.
Mater.. 1998, 9, 390. (0 Mllen, K.; Rabe, J.P. Ann. N.Y. Acad. Sci. 1998, 852,
205.
84. Lakmikantham, M.V.; Vartikar, J.; Kwan, Y.J.; Cava, M.P.; Huang, W.S.;
MacDiarmid, A. Polym. Prepr. (Am. Chem. Soc., Div. Poly. Client.) 1983, 24,
75.
85. Hsieh, B.R. Poly. Bull., 1991, 25, 177.


32
Kowitz and Wegner published results from Suzuki polymerizations using the
more active dichloro[l,r-bis(diphenylphosphino)ferrocene] palladium (II) [PdCb(dppf)]
as catalyst in a THF based solution at room temperature with very high molecular
weights and percent conversion to polymer.67 The methodologies presented in reference
30 were applied to the synthesis of the amine substituted PPP-NEt2-
The synthesis of PdCb(dppf) was first reported in 1984 by Hayashi et al.68 The
PdCbidppf) has two advantages over Pd(OAc)2. The dppf [diphenylphosphino ferrocene]
ligand provides solubility to the catalyst as the polymerization proceeds, thus preventing
contamination of the polymer with black Pd(0). With one objective to increase scale of
the reaction, contamination must be avoided to prevent loss of product during cleaning
steps. A second advantage is that palladium catalysts with bidentate phosphine ligands
are more efficient catalysts than those with unidentate phosphines. The bidentate
phosphine ligands create a unique geometry of the catalyst, minimizing the angle
between the chlorine ligands and somewhat lengthening the palladium to phosphine bond
distance. The bond lengthening reduces steric crowding between the phosphines and the
palladium center. The Cl-Pd-Cl bond angle for two common palladium catalysts with
bidentate ligands, dichloro[l,2-bis(diphenylphosphino)-ethane] palladium (II)
[PdCb(dppe)] and dichloro[l,3-bis(diphenylphosphino)-propane] palladium (II)
[PdCbidppp)]69, along with PdCbidppf) are shown in Figure 2-11. PdCl2(dppf) has the
smallest Cl-Pd-Cl bond angle of the three catalysts (87.8). Experiments by Hiyashi and
coworkers revealed a direct relationship between the Cl-Pd-Cl bond angle and catalyst
efficiency. The two chlorine ligands occupy the sites where the species to be coupled
will eventually reside before reductive elimination. The reduced angle leads to a rate


42
emission between the neutral polymer in THF (plot f), neutral polymer in 1M HC1 (plot
d), and the quatemized polymer in H20 (plot e). Each polymer has a brilliant blue
solution and thin film luminescence with an emission maximum wavelength of ca. 410
nm in THF and water. Intensity of luminescence increases 4 orders of magnitude in the
quatemized PPP-NEt3+[19] over the neutral polymer. This is attributed to the quenching
of the excited state by the lone pair of electrons on the nitrogen sites in the neutral
polymer. Quatemization prevents this quenching mechanism. Figure 2-17 shows the
emission results on a linear intensity scale normalized to 1 for the neutral polymer, PPP-
NEt2[12]. When the plot is viewed in this scaling, it is easily seen that the line shape of
emission is typical of photoluminescent polymers in solution with a broad peak and small
shoulder that tails into higher wavelength regions.
It was theorized that the PPPBP-NEt2[13] would have fewer side chain to
backbone interactions than PPP-NE212] and thus a Xmax at higher wavelength. Optical
absorbance and emission in solution was identical to that of the higher molecular weight
PPP-NEt2[12] samples. UV-Vis absorption measurements were taken on thin films cast
from THF of both PPPBP-NEt2[13] and PPP-NEt2[12], The plots were nearly identical
with an absorption maximum just above 350 nm. If we assume that the oligomeric
PPPBP-NEt2[13] has reached a degree of polymerization such that its maximum
absorption wavelength has been achieved (typically this would be 12-15 rings or only a
degree of polymerization of 4 in this case), the similarity in thin film absorption data
indicates that the alkoxyamine side groups along the backbone of PPP-NEt2[12] are
disturbing the conjugated backbone planarity very little, allowing the conjugated
backbone to maintain a very rigid conformation.


125
ammonium salts and passed through a silica gel plug using an appropriate solvent. After
removal of solvent, the solids were recyrstallized twice from methanol or ethanol.
1.4-Bis((triniethysilyl)ethynyl)-benzene (38). Reagents: 1,4-diidobenzene (3.00
g, 9.1 mmol), trimethylsilylacetylene (2.00 g, 20.0 mmol), PdCl2(PPh3)2 (0.26 g, 0.4
mmol), and Cul (0.03 g, 0.2 mmol). Product was collected as a crude black solid and
purified by column chromatography on silica gel (1:1 hexanes/CH2Cl2) followed by
recrystallization from MeOH giving white crystals (2.21 g, 90% yield), mp. 119-122 UC.
H NMR (300 MHz, CDC13) 7.40 (s, 4 H), 0.25 (s, 18 H) ppm. C NMR (75 MHz,
CDC13) 131.74, 123.14, 104.55, 96.29, -0.03 ppm. Anal. Caled for C,6H22Si2: C, 71.08 ;
H, 8.06. Found: C, 70.45; H, 8.06. FAB-HRMS (M)+ calculated for C16H22S2:
270.1260, Found 270.1255.
1.4-Bis((trimethysilyI)ethynyl)-2,5-bis(hexyloxy)benzene (36). Reagents: 1,4-
bis(hexyloxy)-2,5-diiodobenzene (3.06 g, 5.8 mmol), trimethylsilylacetylene (1.73 g,
17.3 mmol), PdCl2(PPh3)2 (0.41 g, 0.6 mmol), and Cul (0.11 g, 0.6 mmol). Product was
collected as a crude black solid and purified by column chromatography on silica gel (1:1
hexanes/CFFCF) followed by recrystallization from MeOH giving faint yellow crystals
(2.18 g, 80% yield). H NMR (300 MHz, CDC13) 6.89 (s, 2 H), 3.94 (t, 4 H), 1.78 (m, 4
H), 1.50 (m, 4 H), 1.34 (m, 8 H), 0.90 (t, 6 H), 0.25 (s, 18 H) ppm. ''c NMR (75 MHz,
CDCI3) 154.03, 117.33, 114.04, 101.09, 100.02, 69.52, 31.61, 29.32, 25.70, 22.63, 14.05,
-0.03 ppm. Anal. Caled for C28H4602Si2: C, 71.44 ; H, 9.86. Found: C, 70.75; H, 10.09.
FAB-HRMS (M)+calculated for C28H46O2S2: 470.3036, Found 470.3051.
1.4-Bis((trimethysilyl)ethynyl)-2,5-bis(nonyloxy)benzene (37). Reagents: 1,4-
bis(nonyloxy)-2,5-diiodobenzene (2.55 g, 4.2 mmol), trimethylsilylacetylene (1.22 g,


50
weight of ca. 14,000 g mol1 versus polystyrene standards. This class of polymer
possesses a bandgap of ca. 2.4 eV (520 nm), falling between that of poly(/?-phenylene),
3.0 eV (413 nm), and polythiophene, 2.1 eV (590 nm).76 An emission at 525 nm was
present in photoluminescence studies conducted in THF when the polymer solution was
excited with a wavelength of light corresponding to its absorption maximum when the
polymer solution was excited with a wavelength of light corresponding to its absorption
maximum.
Optimization of the Stille Coupling Polymerization
In order to maximize the efficacy of the Stille reaction for polymerizations, a
more detailed study by Yu et al. was conducted in 1995 to examine monomer, catalyst,
and solvent effects on the molecular weight of a variety of conjugated polymers.77 The
organohalides and triflates shown in Table 3-1 and the organotin monomers shown in
Table 3-2 were combined under a variety of conditions in the presence of palladium
catalysts. Polymer repeat unit structures are given in Figure 3-3.
Several general conclusions could be made from the polymers synthesized from
the different combinations of monomers and reaction conditions. Diiodo-substituted
monomers are more reactive than dibromo-substituted monomers. Dialkyl-substituted
phenylene monomers gave higher molecular weights than the more electron rich
dialkoxy-substituted phenylene monomers. The oxidative addition step in a palladium
catalyzed reaction is usually facilitated by electron withdrawing or less electron donating
groups. PPP type polymerizations were found to be poor in all cases with dimeric or
trimeric species formed. In general, the organotin monomer prefers to be electron rich
and the organohalide (or triflate) to be electron deficient.


14
R M + RX -> RR[with Pd(0) catalyst] (1-3)
species, M is a metal (tin, boron, etc.), and X is a halogen or triflate. Palladium catalyzed
reactions of Grignard reagents was first reported by Yamamura et al.23 and then expanded
into a synthetically versatile method by Negishi et al. to include organoaluminum,24
zinc,25 and zirconium reagents.26 Many other organometallic reagents have been used as
nucleophiles for the cross coupling reactions including organolithiums,
organostannanes (Stille),28 organosilicon,29 and organoboron (Suzuki)30 compounds.
Terminal alkenyl (Heck)31 and alkynyl (Sonogashira)2 carbons are also effective for the
reaction, though not organometallic species. Several good reviews are present in the
literature dealing with the reactions, mechanisms, and synthetic utilities.33
General Catalytic Cycles and Mechanism
All of these cross coupling reactions are mechanically and synthetically similar
and the general catalytic cycle will be described in this chapter. More focus on reaction
specifics for the differing coupling reactions will be provided in subsequent dissertation
chapters in which the chemistry involved utilizes the particular method. All of these
coupling reactions proceed through a three step cycle involving 1) oxidative addition of
an aryl halide (or other sp C-X species) to Pd[0]; 2) transmetallation, wherein a second
aryl group is transferred from the metallated species to Pd; and 3) reductive elimination
of a biaryl species (see Figure 1-7). If difunctional metallated and aryl halide reagents
are used, oligomeric and polymeric materials may result. Electron withdrawing groups
facilitate the oxidative addition step, while the nature of the halide or leaving group
affects the reaction rate following the trend I>OTf>BrCl. The transmetallation step
may be rate limiting if the metallated species is sterically hindered.


55
stirring overnight, aqueous extraction, followed by removal of hexane under reduced
pressure revealed a slightly brown solid. The stannylated compound was distilled under
vacuum, and recrystallized twice from pentane to yield white crystals in 69% yield.
The corresponding Suzuki reagent, 2,5-thiophene diboronic acid (22) was
prepared by treating 2,5-dibromothiophene with 2.2 equivalents of Mg, followed by
quenching with an excess of dry trimethylborate. The reaction was stirred overnight and
1M HC1 was added to protonate the di-acid and dissolve all magnesium salts. After an
aqueous/ Et20 extraction, the crude product was precipitated into 1M HC1, collected, and
recrystallized from hot H20. A 40% yield of white crystals was recovered and dried in
vacuo at 100 C for 3 hours. As is the case with boronic acids, purification and drying
were simplified by reacting the di-acid with neopentyl glycol in refluxing benzene in a
transesterification manner to produce the 2,5-thiophene diboronate ester (23) as white
crystals in 70% yield as outlined in Figure 3-5.
2.05 eq. n-BuLi
TMEDA
hexane
reflux, 3 h
2.05 eq. Me3SnCI
RT, overnight
Figure 3-4. Synthesis of 2,5-bis(trimethylstannyl)thiophene.
Due to the lack of literature attempts at polymerizing a thiophene di-boronic acid
or ester, a test coupling procedure was carried out to determine if the reagent would
couple before degradation. A simple three component ring system was chosen instead of
test polymerizations for the study, since too many factors are present in polymerizations


CHAPTER 4
CATIONIC POLY(p-PHEN YLENE-ETH YN YLENE)s
Introduction
Early Synthetic Attempts
Poly(/?-phenyleneethynylene)s [PPEs] are a class of polymers that are composed
of alternating phenyl rings and triple bonds. They are structurally very similar to the
much studied polymer, poly(/?-phenylenevinylene) [PPV], in which electroluminescense
from a conjugated polymer was first observed. PPEs did not receive the early attention
of PPV, but research efforts have increased as the luminescent and conducting properties
82
of PPE have been shown to be useful for explosive detection, molecular wires that
bridge nanogaps,83 and polarizers for liquid crystalline displays.
The first synthesis of PPE oligomers was reported in 1983 and consisted of
heating cuprous acetylide with diiodobenzene to a degree of polymerization of 10-12
84
(Figure 4-la). This type of approach, along with dehydrobromination of halogenated
or
PPVs (Figure 4-lb), and generation of PPE by electrochemical reduction of hexahalo-
p-xylene (Figure 4-lc)86, was unsuccessful in preparing well-defined systems without
defects and solubility of the resulting species was low. PPEs have also been synthesized
by ring-forming polycondensations, such as the reaction of acetylendicarboxylic amides
with hydrazine sulfate in polyphosphoric acid (PPA) followed by thermal cyclization of
the hydrazide groups (Figure 4-Id), and modifications to synthesize a wide variety of
rigid conjugated polyquinolines (Figure 4-le).88
71


35
In order to gain insight into a polymer that mimics "true" PPP more accurately,
PPPBP-NEt2[13] was synthesized (see Figure 2-10). The boronic ester of biphenyl was
coupled with DBNEt using the polymerization conditions determined for PPP-
NEt2(dppf)[12] [PdChidppf), DMF/FFO, and NaHC03]. During the course of the
polymerization, it was noted that the polymeric / oligomeric materials being formed were
precipitating out of solution much earlier than for the PPP-NEt2 reactions. Subsequent
workup revealed only low molecular weight components (Mn < 5000 g/mol) for the
isolated polymer as determined by GPC versus polystyrene standards and a high level
(1.21%) of bromine endgroups as detected by elemental analysis. Only 51% of a tan
material was recovered indicating that the precipitating oligomers are causing an
imbalance in the functional groups present in solution. Without a proper balance of
reactive endgroups in step growth polymerizations, chains will be prevented from
growing into high molecular weight polymers. Insolubility was quickly reached in the
growing PPPBP-NEt2[13] system, as evidenced by early polymer precipitation from the
reaction media.
The low molecular weight and solubility problems of the PPPBP-NEt2[13]
system naturally led to the swinging of the experimental pendulum back to more
substituted phenylene systems. A polymer with every phenylene ring substituted with an
alkoxy-amine side chain should be more soluble during the polymerization and the
subsequent quatemized polymer more water soluble. Figure 2-13 shows two reagents
that could be used in a Suzuki polymerization to achieve the maximum substituted PPP.
The synthesis of compounds 17 and 18 was attempted by the reaction of DBNEt with
magnesium turnings or n-butyllithium followed by quenching with trimethyl borate


58
products such as thiophene and its mono-boronate ester as a result of the higher
temperatures.
Table 3-3. GC/MS results of Suzuki coupling of 2,5-thiophene diboronate ester and 4-
bromotoluene.
Solvent
Temp
Catalyst
Method
Result
THF
RT
PdCl2dppf
1 pot
SM
THF
reflux
PdCl2dppf
1 pot
SM + degradation
Toluene
reflux
PdCl2dppf
1 pot
SM + large degradation
THF
reflux
PdCl2dppf
drop wise
low % mono
DMF
RT
PdCl2dppf
1 pot
low % mono, SM
DMF
72 C
PdCl2dppf
1 pot
Product 24,75%
DMF
72 C
PdCl2dppf
dropwise
Product 24,90 %
DMF
72 C
Pd(OAc)2
dropwise
Product 24,90%
RT = Room Temperature (~22 UC)
SM = Starting Materials (Compound 23 and 4-bromotoluene)
Mono = One tolyl unit coupled to thiophene
The coupling was successful in all cases in which DMF at elevated temperatures
was used. The ability of DMF to coordinate to the catalyst and increase catalytic activity
is believed to account for the success of using this solvent in the reaction. GC/MS
revealed good yields of product 24 for all DMF reactions at 72 C, with excellent yields


116
0.4 (bm, 16.38 H [theo. 18 H]]) ppm. Anal, caled for C24H34N2O2 I.6 C2H5Br2.54
H20: C, 54.02; H, 7.85; N, 4.63; Br, 21.48. Found: C, 52.35; H, 7.61; N, 4.31; Br,
21.40. UV-Vis (H20) A.max 330 nm, log Vnax = 4.17; A,max = 282 nm, log Vnax = 4.02.
PL (H20 with 380 nm excitation) Xmax = 401 nm.
Poly^S-bistl-AjA^Af-triethylammoniurrO-l-oxapropyll-l^-phenylene-fl/-
4,4-biphenylene} dibromide [PPPBP-NEt3+[20]]. A 250 mL single neck round
bottom flask with a magnetic spin bar was charged with PPPBP-NEt2[13] (0.20 g, 0.44
mmol) and stirred at room temperature with bromoethane (5 mL) in THF (20 mL) in a
sealed flask. The partially quatemized amine polymer PPPBP-NEt3+[20] precipitated
out of solution over the course of 5 days. The reaction was poured into acetone and a tan
polymer collected on a medium porosity glass frit. Yield: 0.25 g [85%]. Anal, caled for
C34H48N202Br2: C, 60.27; H, 7.09; N, 4.14; Br, 23.63. Found: C, 65.68; H, 8.05; N,
5.35; Br, 11.98.
Chapter 3
2,5-bis(trimethylstannyl)thiophene (21). The general preparation of this
o 1
compound followed literature procedures followed by a more rigorous purification
needed for polymerization quality monomer. The crude recovered product was distilled
under vacuum (90 UC @ 5 x 10 1 mm Hg) and then recrystallized twice from pentane to
yield a white crystalline solid. Yields for the reaction were slightly less than those
reported in the literature due to the multiple purification steps employed (4.48 g, 69%
yield), mp 100-102 C (lit. mp.81 100-101.6 C) H NMR (300 MHz, CDC13) 7.40 (s, 2


100
(with the use of other bulky bis substituents such as 2-ethylhexyl) and/or create
interesting new materials, especially with the syntheses outlined in Figures 4-9 through 4-
12. Furthermore, the length of the carbon spacing in the starting material 42 could be
adjusted to ultimately provide PPEs with active endgroups at differing lengths from the
conjugated polymer backbone. Such materials would be interesting for possible surface
adsorption studies or energy transfer studies to metallated species covalently attached to
the chain ends.


9
by the other (recombination), and the radiative decay of the excited state (exciton). The
first example of electroluminescence from a conjugated polymer was first reported in
1990 using poly(p-phenylenevinylene)[PPV] as the semiconductor between metallic
electrodes.1-1 In LEDs, a voltage bias is placed across the electrodes at a sufficient level
to achieve injection of positive and negative charge carriers from opposite electrodes and
upon migration, the positive and negative charges combine to form an exciton which
subsequently releases energy as light.
The excitation to form an exciton may also be achieved by exposing the polymer
to light of a wavelength that matches its absorption maximum and is termed
photoluminescence. A singlet exciton is generated by photoexcitation across the
polymers n n* bandgap, and radiatively decays to emit light. Emission spectra for the
same polymer excited either electrically or photolytically are usually very similar,
indicating that the excited state responsible for light generation is identical for both
methods of excitation.
Polaronic excited states are formed along the polymer due to the ability of
polymers to rearrange chain geometry to reduce the strain that can be produced by the
charged excitations (excitons). Polyacetylene has a degenerate ground state allowing
formation of soliton-like chain excitations with a nonbonding n level in the middle of the
n ti* semiconductor gap.14 In polymers with nondegenerate ground states, the two
senses of bond alternation do not have equivalent energies. The charged excitations of a
nondegenerate ground-state polymer are termed polarons or bipolarons and represent
localized charges on the polymer chain. Figure 1-4 shows the nondegeneracy of PPV
along with a schematic representation of an intrachain exciton. Two nonbonding midgap


68
not observed for the PPT-NEt2 polymers. In this case, quatemization led to a decrease in
the emission output of the polymer in solution. Initial data from collaboration work have
indicated that very little light is emitted from devices made from electrostatically
deposited thin solid films of PPT-NEt3+[31] excited by voltage application. Further
work is needed to explain this occurrence, since NMR did not reveal any unexpected
peaks for the polymer post quatemization.
Table 3-6. Summary of optical data for PPT-NEt type polymers.
Polymer
Absorbance
^ max (nm)
Film
Color
Emission
^max (nm)
Emission Color
(Solution)
PPT-
NEt2[28]
460
Red
519
Green
PPT-
NEt3+[31]
411
Red
494
Green
Thermal de-alkylation of the amine sites can occur if the polymer is exposed to
elevated temperatures, thus indicating a dynamic equilibrium at the amine sites. This de
alkylation is evidenced in the TGA for PPT-NEt3+[31] shown in Figure 3-12 where an
initial degradation event starting at 200 C is observed, followed closely by loss of the
triethylamine fragment. The initial weight loss event in the degradation of PPT-NEt2[28]
occurs at 250 C corresponding to the loss of this same triethylamine type fragment. Both
polymers have a final degradation occurring over 400 C, attributed to the breakdown of
the conjugated backbone and little residual mass remains.


113
samples are listed below. JH NMR (300 MHz, CDCI3) 7.71 (bm, 4 H), 7.13 (bm. 2 H),
4.11 (bm, 4 H), 2.87 (bm, 4 H), 2.62 (bm, 8 H), 1.05 (bm, 12 H) ppm. 13C NMR (75.5
MHz, CDCI3) 150.41, 136.98, 130.53, 129.10, 116.32, 68.32,51.98,47.82, 12.03 ppm.
UV-Vis (THF) Amax = 350 nm, log £-max = 3.84; 7max = 290 nm, log £-max = 3.74. UV-
Vis (1M HC1) Amax = 352 nm, log fmaX = 3.98; 290 nm, log VnaX = 3.64. PL (THF with
370 nm excitation) Amax = 435 nm. PL (1 M HC1 with 370 nm excitation) Amax = 408
nm.
PPP-NEt2 (Br-72)[14]. Reagents: DBNEt (0.976 g, 2.09 mmol),
bisneopentylglycol 1,4-phenylenediboronate (8, 0.632 g, 2.09 mmol), Na2CC>3 (1.33g,
12.56 mmol), and Pd(OAc)2 (20 mg, 4 mol %). 25 mL DMF and 5 mL H20 were used as
solvent. Reaction time: 3 days. Yield: 0.61 g [76 %]. Anal, caled for C24H34N202Bro.o26
: C, 74.95; H, 8.91; N, 7.28; Br, 0.53. Found: C, 75.09; H, 8.92; N, 8.05; Br, 0.54. GPC
(CHCI3 vs. PS) Mn = 15,900 gmol*1, MP 24,300 gmol'1, Mw = 35,000 gmol'1,
MjM =2.20.
PPP-NE2 (dppf)[12]. Reagents: DBNEt (1.995 g, 4.28 mmol),
bisneopentylglycol 1,4-phenylenediboronate (8, 1.293 g, 4.28 mmol), NaHCC^ (3.60 g,
42.86 mmol), and PdCl2(dppf) (35 mg, 1 mol %) [Strem Chemicals Inc.]. 50 mL DMF
and 10 mL H20 were used as solvent. Reaction time: 3 days. Yield: 1.552 g [95 %].
Anal, caled for C24H34N202Bro.o26 : C, 74.95; H, 8.91; N, 7.28; Br, 0.53. Found: C,
75.21; H, 8.94; N, 8.01; Br, 0.45. GPC (CHCI3 vs. PS) Mn = 18,700 gmol*1, MP =
19,400 gmol*1, Mw = 22,100 gmol'1, MjMn = 1.18.


119
The DMF solution was concentrated to ~5 mL and precipitated into 150 mL MeOH. A
dark red solid was collected on a medium porosity glass frit and subsequently extracted
with MeOH for 24 hours, acetone for 24 hours, and then collected by extraction with
chloroform (via Soxhlet extraction). The chloroform soluble fraction was collected by
0 i
evaporation of the solvent and dried in vacuo at 50 C overnight. H NMR (300 MHz,
CDC13) 7.63 (bm, 2 H), 7.34 (bm. 2 H), 4.24 (bm, 4 H), 3.04 (bm, 4 H), 2.69 (bm, 8 H),
1.11 (bm, 12 H) ppm. c NMR (75 MHz, CDC13) 149.53, 139.09, 126.49, 123.26,
113.26, 68.36, 52.09, 42.88, 12.01 ppm. UV-Vis (THF) 7.max = 460 nm, log £max =
4.26. PL (THF with 460 nm excitation) Xmax = 519 nm.
PPT-NEt2(48)[25]. Reaction time of 48 hours. Reagents: DINEt (1.0895 g,
1.945 mmol), 2,5-bis(trimethylstannyl)thiophene (21) (0.7967 g, 1.945 mmol), and 32 mg
of PdCl2(PPh3)2 (0.03 mmol). 0.45 g of polymer was recovered (60% yield). Anal, caled
for C22H32N2O2SI0 079: C, 66.33; H, 8.04; N, 7.03; I, 2.52. Found: C, 65.23; H, 7.84; N,
6.65; I, 2.50. GPC (THF vs. PS) M = 3,200 g mol'1, MP = 4,300 g mol'1, M = 5,200
g mol'1, MjMn = 1.70.
PPT-NEt2(96)[26]. Reaction time of 96 hours. Reagents: DINEt (1.2568 g,
2.243 mmol), 2,5-bis(trimethylstannyl)thiophene (21) (0.9191 g, 2.243 mmol), and 37 mg
of PdCl2(PPh3)2 (0.04 mmol). 0.79 g of polymer was recovered (80% yield). Anal, caled
for C22H32N2O2SI0.037: C, 67.13; H, 8.14; N, 7.12; I, 1.19. Found: C, 63.64; H, 8.03; N,
6.46; I, 1.20. GPC (THF vs. PS) M = 4,100 g mol'1, MP = 5,800 g mol'1, M = 6,900
g mol'1, MjMn = 1.68.


29
35% 9
Figure 2-8. Synthesis of di-boronic phenylene reagents for use in Suzuki couplings.
Figure 2-9 outlines the preparation of a three ring model compound that was used
as a guide for assigning peaks in the H and 13C NMR of subsequent polymers and also as
a standard for luminescence sensing studies conducted with Dr. Kirk Schanze and
Benjamin Harrison at the University of Florida.65 Phenylboronic acid and Pd(OAc)2
were used as purchased from Aldrich Chemical Company. Contamination of the product
with Pd(0) does occur when using Pd(OAc)2, as it lacks solubilizing ligands to keep the
catalyst from precipitating. This will be a more difficult issue to address in the polymer
syntheses to follow, but the contamination could easily be removed from the low
molecular weight compound, 10, by the addition of decolorizing carbon and filtration
through sebaceous earth (Celite). Quatemization of compound 10 was achieved by
stirring in THF and bromoethane at 40 C for 3 days. During the course of the reaction,
the desired product, 11, precipitated out of solution. NMR peak values for both can be
found in Chapter 5 (Experimental) of the dissertation. As expected, compounds 10 and
11 display extreme solubility differences. Compound 10 is soluble in relatively non
polar solvents such as halogenated organics (CHCI3 and CH2CI2) and the more polar
THF, while compound 11 is soluble in very polar solvents such as acetonitrile and water.


54
diethylamino)-l-oxapropyl]-l,4-phenylene}-tf/r-2,5-thienylene) (PPT-NEt2) which is
easily converted to the quaternary ammonium salt, poly{2,5-bis[2-(A,/V,A-
triethylammonium)-l-oxapropyl]-l,4-phenylene-a/i-2,5-thienylene} dibromide (PPT-
NE3+). It was also desired to determine if a Suzuki type polymerization would work
using thiophene diboronic reagents. A Suzuki approach would allow for the use of much
less toxic boronic reagents than the tin reagents used in Stille couplings. The results and
discussion following will address these aspects in greater detail.
Results and Discussion
Monomer Syntheses and Suzuki Coupling Test Reactions
In order to effectively synthesize PPT-NEt3+ of high molecular weight via a Stille
or Suzuki polymerization, 2,5-bis(3-[A,Ar-diethylamino]-l-oxapropyl)-l,4-diiodobenzene
(DINEt) (Figure 2-7) and 2,5-bis(trimethylstannyl)thiophene (21) or 2,5-thiophene
diboronic acid (22) as co-monomers were selected. Literature precedent for Suzuki
polymerizations involving thiophene were not present, but success of this type of
polymerization was desired because the aryl tin reagents used in the Stille reaction are
somewhat less reactive as compared to the aryl boronic acids used in the Suzuki
coupling. A diiodobenzene monomer was chosen over a dibromo reagent due to its
higher reactivity in Pd coupling reactions. Particular attention was paid to the stringent
monomer purification requirements needed for complete conversion of functional groups.
The synthesis of 2,5-bis(trimethylstannyl)thiophene (21) by literature
methodology is outlined in Figure 3-4.81 Thiophene was treated with 2.05 equivalents of
n-butyllithium and refluxed in a hexane / TMEDA solution for 30 minutes, cooled to 0 C
in an ice bath, and quenched with 2.05 equivalents of trimethylstannyl chloride. After


61
yield and Mn, while increasing the reaction time to 10 days in PPT-NEt2(240)[27] led to
no appreciable molecular weight enhancement ( Mn of 4,200 g mol1).
Later experiments were fine tuned to account for the possible degradation of the
2,5-bis(trimethylstannyl)thiophene when exposed to elevated temperatures in the reaction
medium. PPT-NEt2(96-drop)[28] was synthesized by slow dropwise addition of 21 to a
solution of catalyst, DINEt, and DMF via an addition funnel over the course of 4 hours
and allowed to run for 96 hours. The reaction was precipitated into MeOH, the crude
polymer recovered by filtration, followed by extraction with MeOH and acetone for 24
hours each, and finally collected by extraction with chloroform (via Soxhlet extractor).
Table 3-4. Gel permeation chromatography results for Stille coupling of PPT-NEt2.
polymer
reaction
solvent
reaction
type
reaction
time
(hours)
K
kg mob1
MP
kg mob1
K
kg mol'1
PPT-NEt2
DMF
Stille
48
3.2
4.3
5.2
1.70
(48)[25]
PPT-NEt2
DMF
Stille
96
4.1
5.8
6.9
1.68
(96)[26]
PPT-NEt2
DMF
Stille
240
4.2
5.4
7.2
1.71
(240)[27]
PPT-NEt2
DMF
Stille
96
5.3
6.9
9.0
1.70
(96-drop)[28]
(dropwise)
GPC results in THF vs. polystyrene standards.
The chloroform soluble fraction constituted an 84% yield and H and l3C NMR
analysis gave expected shift values with the proton peaks appearing as broad multiplets
without defined splitting for all polymeric materials recovered (see Figure 3-8). This
polymer exhibits a Mn of 5,300 g mol'1 (GPC versus PS standards). This methodology


17
these are step growth polymerizations. Catalyst residues and by-products are easily
removed from the polymer product.
In the synthesis of conjugated polymers, several factors influence ultimate
molecular weight properties. A balance must be maintained in a polymerization between
a solvent that will keep the polymer chain in solution, so that additional couplings can be
performed, and that will also solubilize the Pd catalyst so that it remains active. Chain
growth is terminated by premature polymer precipitation. In general, DMF, THF, and
toluene are effective solvents for the coupling reactions, with DMF able to stabilize the
catalysts the most due to its coordination ability. The polarity of the solvent should
match the polarity of the polymer to best keep it in solution. Temperatures must be
carefully monitored as excess thermal energy can degrade the catalyst and promote the
degradation of the active functionalities at the end of the polymer chains, thereby
terminating chain extension. Temperatures at or below 80 C are commonly used.
Conjugated Polyelectrolytes
As mentioned earlier, one important issue in the conjugated polymer field is that
of processability. Traditionally, branched or long alkyl side chains are added to
conjugated polymers to increase solubility. Although this is effective, chlorinated and
high boiling solvents are often necessary to dissolve the polymers. One approach to
overcoming this difficulty is to create polar conjugated polymers that are water soluble.
The interesting luminescent properties mentioned previously will still be present, but now
the polymers may be processed from the more environmentally and industrially friendly
solvents, such as ethanol, water, etc. Side chains can be functionalized with carboxylate,
sulfonate, and quatemized ammonium groups to achieve the water solubility.


SYNTHESIS OF VARIABLE BANDGAP CONJUGATED POLYELECTROLYTES
VIA METAL CATALYZED CROSS-COUPLING REACTIONS
By
MICHAEL BRIAN RAMEY
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
2001


80
the appropriate starting di-iodide compound as light yellow or white crystals. Elemental
analysis results for compounds 39-41 are listed in Table 4-1.
pCgHi3
OC6H
13
TMS(/ \E^-TMS
H-
Hi3C60 34
2.2 eq.
Hi3C60 36
or
H 1= Si-
\
PdCI2(PPh3)2
Cul
Et3N
A
OC6Hi3
-p-
Hi3C60 39
or
-H
TBAF or aq. KOH
THF
H
TMS(/ V^TMS
H-
-H
38
41
Compound % Yield
39 75
40 70
41 82
Figure 4-8. Synthesis of various 1,4-diethynylphenylene monomers.
The previously described di-iodide compound 2,5-bis(3-[/V,./V-diethylamino]-l-
oxapropyl)-l,4-diiodobenzene (DINEt) was used in conjunction with the above di-
ethynyl compounds for Sonogashira polymerizations to provide a functional amine site to
be quatemized after polymerization (see Chapter 1). Synthesis of 2,5-bis(3-[AfiV-
diethylamino]-l-oxapropyl)-l,4-diethynylbenzene, produced by Pd(0) coupling of DINEt
with trimethylsilylacetylene and treatment with base, was attempted in order to have a
companion reagent to DINEt, which upon Sonogashira polymerization with DINEt
would produce a PPE with every phenylene ring possessing alkoxyamine side chains.


104. (a) Rau, I.U.; Rehahn, M. Acta Polymer. 1994,45,3. (b) Brodowski, G.
Horvath, A.; Ballauff, M.; Rehahn, M. Macromolecules 1996, 29, 6962.
105. Huenig, S.; Bau, R.; Kemmer, M.; Meixner, H.; Metzenthin, T.
Eur.J.Org.Chem. 1998, 2, 335.
106. Saraf, T. Pak. J. Sci. lnd.Res. 1972, 15, 160.


fan, workout partner, and scientific consultant; and C.J. Dubois who is one entertaining
Cajun, but respectful and competent lab co-worker.
IV


2-10. Suzuki polymerizations for neutral alkoxy-amine containing PPPs 31
2-11. Cl-Pd-Cl bond angle for PdCLCdppe), PdC^idppp), and PdCLCdppf) catalysts 34
2-12. Gel permeation chromatogram for PPP-NEt2(dppf)[12] 36
2-13. Envisioned boronic reagents for a more substituted PPP-NEt2 polymer 38
2-14. Pd catalyzed coupling to diboronic reagents for Suzuki couplings 38
2-15. Quatemization of PPP-NEt2 40
2-16. UV-Vis / Emission behavior of neutral and water soluble PPP-NEt 43
2-17. Photoluminescent spectrum of PPP-NEt2[12] in THF with normalized and linear
emission scale 44
2-18. TGA thermograms for neutral and water soluble PPP-NEt under N2 45
3-1. Literature examples of phenylene-co-thiophene type polymers 49
3-2. General scheme for the Stille polymerization 49
3-3. Representative polymer repeat units of Stille polymerizations 52
3-4. Synthesis of 2,5-bis(trimethylstannyl)thiophene 55
3-5. Synthesis of 2,5-thiophene diboronate ester 56
3-6. Test coupling reaction of 2,5-thiophene diboronate ester and 4-bromotoluene 57
3-7. Stille coupling polymerization scheme for PPT-NEt2 60
3-8. 'H and l3C NMR spectra of PPT-NEt2[28] 63
3-9. Synthesis of PPT-NEt2[29] via Suzuki coupling polymerization 64
3-10. Quatemization of PPT-NEt2 to form PPT-NEt3+ 66
3-11. Normalized UV-Vis absorption and solution photoluminescence for PPT-NEt type
polymers 67
3-12. TGA thermograms for neutral and water soluble PPT-NEt under N2 69
4-1. Early synthetic methodologies toward poly(/?-phenyleneethynylene)s [PPE] 72
4-2. General reaction scheme for the Heck-Cassar-Sonogashira-Hagihara reaction 73
4-3. Activation of Pd(II) compound to active Pd(0) catalyst 74
IX


44
Figure 2-17. Photoluminescent spectrum of PPP-NEt2[12] in THF with normalized and
linear emission scale.
fact that the thermal degradation of these alkoxy substituted PPPs is a relatively clean
process may provide a route to hydroxylated PPPs. Samples of PPP-NEt2[12] heated to
300 for 10 min were no longer soluble in CHCI3 or THF, but did possess blue
photoluminescence when exposed to ultraviolet light. Treatment of PPP-NEt2[12] with
BB1-3 (a reagent known for its ability to cleave aryl ethers) also resulted in a material
insoluble in CHCI3 or THF with the above mentioned emission characteristic.
Conclusions
An interesting water soluble poly(/?-phenylene) (PPP-NEt3+[19]) has been
synthesized by a variety of modifications of Suzuki polymerization techniques. The use


88
Initial synthetic attempts at producing useful PPEs were performed with the
coupling of DINEt to 1,4-diethynylbenzene using toluene / diisopropylamine solvent
system (0.05M in DINEt) and 5 mol% Pd(PPfi3)4 / Cul catalysts (PPE-NEt2/H[51]). A
slight excess of di-ethynyl compound is used (~1 mol %), even with an initial Pd(0)
catalyst, to account for unavoidable side reactions of the compound. After a reaction time
of 24 hours, a noticeable amount of material was precipitating from the reaction flask.
After cooling the reaction after 48 hours, the mixture was poured into cold ethanol and a
yellow solid recovered in nearly quantitative yield. This yellow material was insoluble in
hot chloroform, THF, or toluene. This result was not unexpected as PPEs are known for
their high susceptibility to packing when isolated as solids and subsequent poor
solubility. PPE-NEt2/H[51] was extracted with hot ethanol overnight, in an attempt to
remove catalyst residues. The polymer did appear to swell with solvent and was dried
overnight under vacuum. Elemental analysis was performed on the polymer sample to
help determine if crosslinking had occurred during polymerization. Carbon, hydrogen,
and nitrogen values are close to the predicted values for the polymer repeat unit structure.
Determination of molecular weight (via H NMR or GPC) was excluded by the
insolubility of the material. Elemental analysis of the material was consistent with the
proposed repeat unit structure (see Table 4-1).
Longer alkoxy groups were then used on the di-ethynyl reagent in hopes of
adding solubility in organic solvents to the neutral PPEs. Polymerization of compound
39, l,4-diethynyl-2,5-bis(hexyloxy)benzene, with DINEt under the same conditions as
listed above for PPE-NEt2/H[51] was undertaken (PPE-NEt2/OC6[52]). Over the
coarse of 24 hours, the growing polymer remained in solution with no evidence of a


25
Figure 2-4. Cationic poly(/?-phenylene)'s reported in the literature (R = hexyl).
Due to the important applications available for PPP-NEt3+, it was evident that a
closer inspection of the synthesis, along with scale-up procedures was needed. In
particular, a focused look at a new palladium catalyst with stabilizing ligands and higher
reactivity was a primary concern. Other synthetic investigations to be accomplished were
the effect of the halogenated monomer on the molecular weight of the polymer and the
effect of more unsubstituted phenylene rings in the polymer backbone. With more
unsubstituted phenylene rings, a system that resembles pure PPP better might be
created, but problems of solubility could arise also. The results and discussion following
will address these aspects in greater detail.
Results and Discussion
Monomer and Model Compound Syntheses
Previous work had shown that the most promising route for the cationic water
soluble PPP synthesis was to first create a neutral PPP analog and then quatemize the
amine sites post polymerization. Figures 2-5 and 2-6 show the syntheses of 2,5-
diiodohydroquinone and 2,5-dibromohydroquinone, respectively. 1,4-dimethoxybenzene


LIST OF TABLES
Table Page
1-1. Brief Summary of Emission Wavelength for Differing Conjugated Polymer
Structures 12
2-1. Catalyst effect on the molecular weight properties of PPP-NEt2 polymers 36
2-2. Elemental Analysis results for PPP monomers and polymers 37
2-3. Effect of DBNEt or DINEt on the molecular weight of PPP-NEt2 polymers 38
3-1. Structures of the organohalides and triflates for the Stille reactions 51
3-2. Structures of the organotin monomers for the Stille reactions 51
3-3. GC/MS results of Suzuki coupling of 2,5-thiophene diboronate ester and 4-
bromotoluene 58
3-4. Gel permeation chromatography results for Stille coupling of PPT-NEt2 61
3-5. Elemental Analysis results for PPT monomers and polymers 62
3-6. Summary of optical data for PPT-NEt type polymers 68
4-1. Elemental analysis results for PPE monomers and polymers 81
4-2. Summary of optical data for PPE-OC9(20) type polymers 97
vii


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
SYNTHESIS OF VARIABLE BANDGAP CONJUGATED POLYELECTROLYTES
VIA METAL CATALYZED CROSS-COUPLING REACTIONS
By
Michael Brian Ramey
May 2001
Chairman: Dr. John R. Reynolds
Major Department: Chemistry
Metal catalyzed coupling reactions such as the Stille, Suzuki, and Sonagashira
(Heck) have become useful tools for the organic chemist over the past two decades for
the formation of carbon-carbon bonds. Tolerance of functional groups, reasonable
reaction temperatures, and high yields have allowed these techniques to be applied to the
synthesis of conjugated polymers. These syntheses offer access to a wide variety of
conjugated backbone structures that have previously been difficult to reach using
traditional polymerization techniques.
Poly(p-phenylene) [PPP], poly(/?-phenylene-c6>-thiophene) [PPT], and poly(p-
phenylene-co-ethynylene) [PPE] electrolytes have been prepared by using one of the
aforementioned coupling techniques. A methodology was applied whereby charge neutral
polymers were first synthesized and then converted to the corresponding cationic
polyelectrolyte. This pre-polymer technique allows for studies comparing neutral
polymer properties (i.e., absorption, luminescence, solubility) to those of the
xi


CHAPTER 1
INTRODUCTION
The Origination of Polymer Chemistry
Over the past 100 or so years, polymer science and chemistry have evolved from
early rubber and Bakelite type chemistries to extensively characterized and
commercialized materials. Looking back on the early evolution of this branch of science,
todays observer would find vigorous debates on the exact nature of polymers: were they
linear polymers held together in long chains by covalent bonds or merely
agglomerations of smaller molecules held together by ionic forces? Today, we know
that they are indeed based on the first principle as proposed and defended by Staudinger.1
Necessity proved to be the mother of invention as the need to replace natural
items such as silk (Nylon 6,6) and rubber (cis- 1,4-polybutadiene), imported from foreign
countries to the United States, was of utmost importance during World War II as the
conflict threatened to cut off supplies. From these beginnings, the study and everyday
use of man-made polymers has exploded (possibly best exemplified by the whispering of
the line Just one word: plastics in the 1967 Hollywood movie The Graduate).
Synthetic polymers are a major cornerstone of the entire industrial chemical world and
basic research on these materials has enabled scientists to understand natural polymers,
such as proteins, on deeper levels than ever before. With such broad and sweeping
applications and variations throughout polymer chemistry, a complete overview of the
science would be impossible; therefore, a guided tour will be presented herein outlining
1


96
(normalized for convenience). It is interesting to note the dramatic shift in absorbance
maximum between the neutral and charged polymers. PPE-NEt2/OC9(20)[54] exhibits a
A,max at 442 nm with a corresponding molar absorptive of about 43,000 L mol'cm'1, while
PPE-NEt2H+/OC9(20)[55]s A,max is blue shifted 34 nm to 408 nm with a corresponding
molar absoiptivity of about 110,000 L mol'em"1. Fine tuning of the A.max in solution
could be achieved by controlling the pH of the solution (assuming that polymer solubility
in a suitable solvent can be maintained), as incomplete prolongation would lead to a
lower extent of hypsochromic shift.
The solution emission results revealed a dramatic increase in the emission
intensity for the protonated polymer when compared to the neutral PPE, much like that
seen in Chapter 2 for the PPP-NEt polymers. Quantum yields were obtained for each
polymer relative to perylene with a quantum yield of 0.94 revealing a value of only 0.001
for PPE-NEt2/OC9(20)[54] and a dramatic increase to 0.86 for the protonated PPE-
NEt2H+/OC9(20)[55]. Each polymer has a blue-green solution luminescence at 502 nm
for PPE-NEt2/OC9(20)[54] and 464 nm for PPE-NEt2H+/OC9(20)[55], The increase in
quantum yield is attributed to the prevention of quenching of the excited state by the lone
pair of electrons on the nitrogen by protonation. The dramatic change in emission when
the amine sites are protected makes these polymers excellent candidates for H+ or
alkylating agent sensors. Table 4-2 summarizes the optical properties for the PPE-
OC9(20) polymers.


123
1.4-Bis(hexyloxy)benzene (32). Reagents: Hydroquinone (10.41 g, 94.6 mmol),
hexylbromide (62.5 g, 378.5 mmol), and KOH (42.40 g, 757.0 mmol). Product was
collected as a crude brownish solid and was recrystallized from ethanol giving 21.84 g of
a white, crystalline material (83% yield), mp. 43-45 C. H NMR (300 MHz, CDC13)
6.82 (s, 4 H), 3.89 (t, 4 H), 1.75 (m, 4 H), 1.34-1.44 (bm, 12 H), 0.90 (t, 6 H) ppm. "c
NMR (75 MHz, CDC13) 153.12, 115.33, 68.62, 31.89, 29.56, 26.07, 22.70, 14.13 ppm.
1.4-Bis(nony!oxy)benzene (33). Reagents: Hydroquinone (3.99 g, 36.3 mmol),
nonylbromide (22.53 g, 108.8 mmol), and KOH (16.24 g, 290.0 mmol). Product was
collected as a crude brownish solid and was recrystallized from ethanol giving 10.33 g of
a white, crystalline material (79% yield), mp. 56-58 C. H NMR (300 MHz, CDC13)
6.82 (s, 4 H), 3.89 (t, 4 H), 1.75 (m, 4 H), 1.34-1.44 (bm, 12 H), 0.90 (t, 6 H) ppm. "c
NMR (75 MHz, CDC13) 153.12, 115.33, 68.62, 31.89, 29.56, 29.42, 29.28, 26.07, 22.70,
14.13 ppm.
General procedure for the iodination of 1,4-dialkoxybenzenes. A 250 mL, 3
neck round bottom flask was charged with 1,4-dialkoxybenzene and a solvent system
consisting of 90:7:3 HOAc/ H2O/ H2SO4 by volume. CHCI3 was added until the 1,4-
dialkoxybenzene dissolved. I2 and KI04 were added and the reaction heated to 70 C
overnight. The reaction was cooled, poured into 500 mL H2O, and extracted with
chloroform (3 x 150). The combined organics were dried over MgSCL and the solvent
evaporated. Purification was accomplished by recrystallization or column
chromatography, depending on the compound.
1.4-Bis(hexyloxy)-2,5-diiodobenzene (34). Reagents: 1,4-
Bis(hexyloxy)benzene (13.43 g, 48.3 mmol), I2 (15.07 g, 58.0 mmol), and KIO4 (13.33 g,


97
Table 4-2. Summary of optical data for PPE-OC9(2Q) type polymers.
Polymer
Absorbance
^ max (nm)
Film
Color
Emission
^>max (nm)
Emission Color
(Solution)
Quantum
Yield
PPE-NEt2
/OC9(20)
[54]
442
Orange
502
Blue-Green
0.001
PPE-
NEt2H+
/OC9(20)
[55]
408
Orange
464
Blue-Green
0.86
c
£
E
c
o
CO
CO
E
LU
O
CD
O
c
03
-Q
O
CO
X)
<
Figure 4-18. Normalized UV-Vis absorption and solution photoluminescence for PPE-
OC9(20) type polymers.
a) PPE-NEt2H+/OC9(20)[55] UV-Vis absorption in EtOH.
b) PPE-NEt2/OC9(20)[54] UV-Vis absorption in CHC13.
c) PPE-NEt2H+/OC9(20)[55] emission in EtOH.
d) PPE-NEt2/OC9(20)[54] emission in CHCI3.


85
i i
4 6 8 10 min
Figure 4-10. Gas chromatography analysis of purification of 6-bromohexylmethylether
(43) by vacuum distillation using (a) simple vigreux column and (b) spinning band
column.


112
H, 8.76; N, 6.08. Found: C, 78.41; H, 9.56; N, 5.90. FAB-HRMS (M+) calculated for
C30H40N2O2: 460.3090, Found 460.3111.
l,4-Diphenyl-2,5-bis(3-[N,AyV-triethylammonium]-l-oxapropyl)phenylene
dibromide (11). Compound 7 (0.22 g, 0.5 mmol) was dissolved in THF and stirred with
15 mL of bromoethane for 2 days. The solution became cloudy during the course of the
reaction. A white solid (0.21 g, 0.3 mmol) was collected by precipitation into hexane and
dried in vacuo overnight. The new material was highly soluble in acetonitrile and water
indicating a successful reaction of the neutral compound 10. Yield 0.210 g [65%]. *11
NMR (300 MHz, D20) ppm. 7.27 (bm, 4 H), 6.82 (s, 2 H), 4.00 (t, J = 4.2 Hz, 4 H), 3.25
(t, J = 4.2 Hz, 4 H), 2.91 (q, J = 7.2 Hz, 12 H), 0.95 (t, J = 7.2 Hz, 18 H) ppm. Anal,
caled for C34H50N2O2B1-2: C, 60.34; H, 7.45; N, 4.14; Br, 23.34. Found: C, 61.27; H,
7.67; N, 4.29; Br, 22.54. FAB-HRMS (M+) calculated for C34H5oN202Br2: 676.2239,
Found 676.2965
General Procedure for Suzuki Polymerization Preparation of Poly({2,5-bis[2-
(A^A-diethylamino)-l-oxapropyl]-l,4-phenylene}-a/f-l,4-phenylene) [PPP-NE2].
Organic solvent and H2O (5:1 v/v) were sparged with argon for 1 hour. A Schlenk flask
with a magnetic spin bar was charged with DBNEt or DINEt, bisneopentylglycol 1,4-
phenylenediboronate (8), carbonate base, and Pd (II) catalyst. The flask was evacuated
and backfilled with argon three times. The solvent was added via cannula to the flask
and the reaction was heated to 75C and stirred for an appropriate amount of time. The
solution was precipitated into 200 mL of cold methanol and collected on a glass fnt. The
polymer was washed with methanol then water, dried in an air stream, then dried in
vacuo at 60C overnight. NMR and optical data that are identical for all PPP-NEt2


26
(4) was iodonated under acidic conditions using potassium periodate, iodine, and a mixed
solvent system consisting of 90:7:3 HO Ac/ H20/ H2S04by volume with heating to yield
2,5-dimethoxy-l,4-diiodobenzene (5).61 Compound 5 was reacted with boron tribromide
in methylene chloride at -78 C, producing 2,5-diiodohydroquinone (DIHQ).62 It
should be noted that boron tribromide is a very reactive reagent with large amounts of
HBr gas liberated during the aqueous workup of the reaction. DIHQ is recovered as a
crude brown solid. Recrystallization from THF and hexane affords colorless crystals of
pure product. Both steps are high yielding (81% and 76%) with an overall 62% yield
based on starting material 4. Analysis of the crude material by H NMR shows the only
organic product was the desired compound 4. It was later found that use of this brown
material was sufficient for the Williamson etherifications to follow. 90 % yield of the
crude material was obtained.
h3co
OCH,
kio4,i2
AcOH / H20 / H2S04
70 C/ 12 h
76%
Figure 2-5. Conversion of 1,4-dimethoxybenzene to 2,5-diiodohydroquinone.
2,5-dibromohydroquinone (DBHQ) was synthesized in 40% yield from the direct
bromination of hydroquinone (6) in methylene chloride and acetic acid. The reaction
proceeds through three stages. The initial setup involves the suspension of hydroquinone
in the solvent system. As the first equivalent of bromine is added, the resulting
monobrominated species enters solution and as the second bromine adds to the phenyl
ring, the desired product precipitates out of solution making product recovery a simple


Monomer Syntheses and Suzuki Coupling Test Reactions 54
Neutral Polymer Syntheses 59
Polymer Quatemization 65
Physical Properties of PPT Type Polymers 66
Conclusions 69
CATIONIC POLY(p-PHEN YLENE-ETH YN YLENE)s 71
Introduction 71
Early Synthetic Attempts 71
Palladium (0) Coupling Reactions 72
Dialkoxy-Poly(p-phenyleneethynylene)s 75
Results and Discussion 78
Monomer Syntheses 78
Neutral Polymer Syntheses 87
Polymer Quatemization 94
Physical Properties of PPE Type Polymers 95
Conclusions 99
CONCLUSIONS 101
EXPERIMENTAL 107
Chapter 2 108
Chapter 3 116
Chapter 4 122
REFERENCES 132
BIOGRAPHICAL SKETCH 140
vi


130
7.89; N, 4.01. A small portion of the polymer precipitated during the reaction. 100 mg
of soluble material could be extracted with an excess of boiling chloroform after
precipitation and drying.
Polymer PPE-NE2/OC9 (High)[53]. Reagents: DINEt (0.3738 g, 0.667
mmol), l,4-diethynyl-2,5-bis(nonylloxy)benzene (40) (0.2792 g, 0.6805 mmol), Cul (6.2
mg, 0.033 mmol)and 38.4 mg of Pd(PPh3)4 (0.033 mmol). 0.472 g of polymer was
recovered (99% yield). Anal, caled for C46H70N2O4: C, 77.27; H, 9.87; N, 3.92. Found:
C, 76.11; H, 9.79; N, 3.47; I, 0.55. The polymer formed a gel during the reaction,
which was dissolved with excess chloroform. After precipitation, washing, and drying,
the polymer was completely insoluble in any common organic boiling solvent.
Polymer PPE-NE2/OC9 (20)[54]. Reagents: DINEt (0.3685 g, 0.658 mmol),
l,4-diethynyl-2,5-bis(nonylloxy)benzene (40) (0.2753 g, 0.671 mmol), iodobenzene (7.2
mg, 0.035 mmol), Cul (6.3 mg, 0.033 mmol) and 38.0 mg of Pd(PPh3)4 (0.033 mmol).
0.44 g of polymer was recovered (99% yield). Anal, caled for C46H70N2O4: C, 77.27; H,
9.87; N, 3.92. Found: C, 75.80; H, 9.58; N, 3.45. The polymer remained soluble during
the reaction and upon precipitation and complete drying a small amount of material was
soluble in chloroform. The experiment was conducted a second time using the conditions
above and the polymer was collected via gravity filtration through coarse filter paper and
only air dried. The solvated polymer displayed much greater solubility allowing for
more complete analyses and conversion to the cationic polyelectrolyte. JH NMR (300
MHz, CDCI3) 7.04 (bs, 2 H), 7.02 (bs. 2 H), 4.12 (bm, 4 H), 4.03 (bm, 4 H), 2.98 (bs, 4
H), 2.68 (bm, 8 H), 1.87 (bm, 4 H), 1.52 (bm, 4 H), 1.26 (bm, 20 H), 1.06 (bm, 12 H),
0.88 (bt, 6 H); Endgroup 7.55 (m, 0.17 H) ppm. 13C NMR (75.5 MHz, CDCI3) 153.44,


60
DINEt
Polvmer
Time
Method
PPT-NEt2(48) [25]
48 h
1 pot
PPT-NEt2(96) [26]
96 h
1 pot
PPT-NEt2(240) [27]
240 h
1 pot
PPT-NEt2(96-drop) [28]
96 h
dropwise
Figure 3-7. Stille coupling polymerization scheme for PPT-NEt2.
Reactions were conducted under varied conditions to determine the optimal
needed to achieve the highest molecular weight possible for PPT-NE2. The first set of
reactions were earned out as one pot syntheses, where the stannylated compound,
DINEt, and DMF were mixed together and heated to 70 C. PdCl2(PPh3)2 was then
added in one portion in a catalytic amount to the reaction flask. PPT-NEt2(48)[25] and
PPT-NEt2(96)[26] were synthesized with 48 and 96 hour reaction times followed by
precipitation into MeOH. During the polymerization, polymer was seen to precipitate out
and coat the reactor. PPT-NEt2(48)[25] was collected in75% yield with a Mn of 3,200
g mol'1,while PPT-NEt2(96)[26] was collected in 80% yield with a Mn of 4,100 g mol"1
(GPC versus PS standards)(see Table 3-2). Polydispersities of 1.7 were found for both,
but with the extensive fractionation during purification this value is not indicative of the
initial polymerization. Doubling the reaction time lead to a modest improvements in both


LIST OF FIGURES
Figure Page
1-1. Structures of poly(/?-phenyleneterephthalamide) (1), poly(benzobisthiazole) (2), and
poly(p-phenylene) (3) 3
1-2. Application of Frosts circle to illustrate the energies of molecular orbitals within
cyclic systems 5
1-3. Band structure and density of states (DOS) diagram of a simple one dimensional
metal (polyacetylene) prior to and after a Peierls distortion 7
1-4. Geometrical relaxation of a PPV chain in response to photo- or electo- excitation 10
1-5. Polaron, bipolaron, and singlet exciton energy levels in a non-degenerate ground-
state polymer 10
1-6. Electronic transitions in a conjugated polymer (i.e. PPV) showing both singlet and
triplet states 11
1-7. General catalytic cycle for Pd(0) cross coupling reactions 15
2-1. Synthetic methods to poly(p-phenylene) 22
2-2. Suzuki coupling approaches to substituted poly(/?-phenylene) 23
2-3. Anionic poly(/?-phenylene)'s reported in the literature 24
2-4. Cationic poly(p-phenylene)'s reported in the literature (R = hexyl) 25
2-5. Conversion of 1,4-dimethoxybenzene to 2,5-diiodohydroquinone 26
2-6. Bromination of hydroquinone in the 2,5 positions 27
2-7. Williamson etherification of DIHQ or DBHQ 28
2-8. Synthesis of di-boronic phenylene reagents for use in Suzuki couplings 29
2-9. Synthesis of neutral and cationic PPP model compounds 30
viii


15
X = I, Br, etc.
M = B(OR)2, SnR3 etc.
Figure 1-7. General catalytic cycle for Pd(0) cross coupling reactions.
Reactions are conducted under anaerobic conditions in a variety of solvents such
as THF, DMF, and toluene. For the Suzuki reaction, water and base are added to
accelerate the formation of a more active boronate anion for the transmetallation step;
otherwise the other methods are performed in dry solvent. Pd(II) catalysts such as
PdCl2(PPh3)2 are usually employed in the reactions due to their general storage and
handling advantages over Pd(0) catalysts, such as Pd(PPh3)4, which are air and moisture
sensitive. When using a Pd(II) compound, the reduction of the Pd(II) species to Pd(0)
must occur before the cycle can begin. The exact nature of this conversion is debated but
may include the homo-coupling of the metallated species. Ligands present on the Pd aid


40
frame of days with only minimal precipitation of polymer from solution observed on
samples stored over a month.
Figure 2-15. Quatemization of PPP-NEt2.
PPPBP-NEt2[13] was subjected to the same quatemization conditions as shown
in Figure 2-15. Complete quatemization of this material was not achieved as the neutral
material was difficult to dissolve in the quatemization media. H NMR analysis of the
material was unsuccessful due to the poor solubility in common deuterated solvents.
Elemental analysis (Table 2-2) of the oligomers revealed a 11.98 weight percent of
bromine. Of this amount 10.77% of bromine is due to quatemized ammonium sites and
1.21% is inherent from the parent PPPBP-NEt2[13]. Full quatemization of all amine
sites would require 23.63% bromine. Overall, this indicates that approximately half of
the amine sites were quatemized. The resulting quatemized oligomers were no longer
soluble in CHCI3 or THF, but had reasonable solubility on the order of 5 x 10 M (based
on repeat unit MW) in warm acetonitrile or DMSO. Cloudy suspensions in neutral
H20 were formed in the 10" M concentration range. The polymer was soluble in water
only if the pH was lowered to around 2 or 3.


18
There are also numerous chain extension and folding effects to be studied that are
unique to polyelectrolytes. Flexible polyelectrolytes have been the focus of a
considerable amount of research for many decades.34 Decreasing the ionic strength of a
dilute aqueous solution of polyelectrolyte leads to an expansion of the polymer coils and
an increase of solution viscosity due to strong intra- and inter-molecular forces.
Separation of the intra- versus inter- molecular forces is a difficult experimental task and
only recently has the understanding of the single chain behavior of flexible
polyelectrolytes been achieved by Monte Carlo simulations.'0
Conjugated, stiff-chain polyelectrolyes remain in an extended conformation
regardless of the ionic strength of the solution. Effects observed from lowering the ionic
strength of the system must therefore be due to intermolecular forces. Conjugated
polyelectrolytes represent interesting models for studying the screened coulombic
interactions in polymeric systems. Interesting applications may also be available for
these materials in membrane manufacturing.36 Specifics and references for literature
examples of conjugated polyelectrolytes synthesized by palladium (0) catalysis will be
given in the introduction to Chapter 2.
Scope of the Dissertation
This body of work focuses on incorporation of quatemized 2,5-dialkoxyamine-
phenylene or quatemized 2,5-dialkylamine-phenylene salt moieties into the backbone of
conjugated polymers. Suzuki, Stille, Sonagashira (Heck), and ADIMET polymerization
techniques will be used to synthesize neutral polymers of the following types: poly(/?-
phenylene)[PPP], poly(/?-phenylene-co-thiophene)[PPT], and poly(/?-phenylene-co-
ethynylene)[PPE], whereby the phenylene portion of the repeat unit is initially


.mi
UNIVERSITY OF FLORIDA
3 1262 08554 4509


74
species as outlined in Figure 4-3. Two molecules of a cuprated alkyne transmetallate the
Pd catalyst precursor and a symmetrical butadiyne is reductively eliminated, leaving an
active Pd(0) catalyst. PdCl2(PPh3)2 is used in 0.1-5 mol % amounts and varying amounts
of Cul are used as an alkynyl activator.90 Activation of the Pd(II) catalyst requires
consumption of the alkyne reagent which must be adjusted accordingly in
polymerizations to ensure a 1:1 stoichiometric balance with the haloaromatic compound.
A possible approach to solving the stoichiometric balance problem is the pre-activation
of the catalyst by addition of a monofunctional alkyne (such as phenylacetylene) to the
Pd(II) catalyst, thereby converting it to Pd(0). The catalyst solution could then be added
to the polymerization reagents and the diyne by-product of the catalyst activation would
not interfere with the stoichiometric balance.
Reductive Elimination
Product
Figure 4-3. Activation of Pd(II) compound to active Pd(0) catalyst.


CHAPTER 7
REFERENCES
1. Staudinger, H. Die Hochmolecularen: Springer-Verlag: Berlin, 1932.
2. Ito, T.; Shirakawa, H.; Ikeda, S. J. Polym. Sci., Polym. Chem. Ed. 1974, 72, 11.
3. Lieser, G.; Wegner, F.; Mller, W.; Enkelmann, V.; Meyer, W.J. Makromol.
Chem. Rap. Commun. 1980, 7, 621.
4. Frost, A.A.; Musulin, B. J. Chem. Phys. 1953, 27, 572.
5. Jahn, H.A.; Teller, E. Proc. Roy. Soc. 1937, A161, 220.
6. Peierls, R.E. In Quantum Theory of Solids-, Oxford Univ. Press: London 1955; p
108.
7. Williams, J.M. In Adv. lnorg. Chem. Radiochem. 1983,26,235.
8. (a) Shirakawa, H.; Louis, E.J.; MacDiarmid, A.G.; Chiang, C.K.; Heeger, A.J. J.
Chem. Soc., Chem. Commun. 1977, 578. (b) Chiang, C.K.; Druy, M.A.; Gau,
S.C.; Heeger, A.J.; Louis, E.J.; MacDiarmid, A.G.; Park, Y.W.; Shirakawa, H. J.
Am. Chem. Soc. 1978, 100, 1013.
9. Su, W.P.; Schrieffer, J.R.; Heeger, A.J. J. Phys. Rev. Lett., 1979, 42, 1698.
10. Maarman, H.; Theophilou, N. Synth. Met., 1987, 22, 1.
11. Handbook of Conducting Polymers', Skotheim, T.A.; Elsenbaumer, R.L.;
Reynolds, J.R., Eds.; Marcel Dekker: New York, 1998.
12. Pope, M.; Kallmann, H.; Magnante, P. J. Chem. Phys. 1963, 38, 229.
13. Burroughes, J.H.; Bradley, D.D.C.; Brown, A.R.; Marks, R.N.; Mackay, K.;
Friend, R.H.; Bum, P.L.; Holmes, A.B. Nature 1990, 347, 539.
14. (a) Su, W.-P.; Schrieffer, J.R.; Heeger, A.J. Phys. Rev.Lett.. 1979, 42, 1698. (b)
Su, W.-P.; Schrieffer, J.R.; Heeger, A.J. Phys. Rev. B. 1980, 22, 2099. (c) Rice,
M.J. Phys. Lett. A 1979, 77, 152.
15. (a) Shuai, Z.; Brdas, J.L.; Su, W.P. Chem. Phys. Lett. 1994, 228, 301. (b)
Beljonne, D.; Shuai, Z.; Friend, R.H.; Brdas, J.L. J. Chem. Phys. 1995, 102,
2042.
132


129
General Sonogashira Polymerization Procedure for Poly(/?-
phenyleneethynylene)s (PPE-NEt/R). The appropriate 1,4-diethynyl compound (1.02
equivalents), DINEt, Pd(PPh3)4 (5 mol%), and Cul (5 mol%) are placed in a dry 50 mL
Schlenk flask and evacuated and backfilled with Ar three times. A 2:1 by volume
solution of thoroughly sparged toluene and diisopropylamine solvent system was added
to the reaction via syringe in an amount making the reaction 0.05 M in DINEt. The
reaction was heated to 70 C for 24 hours. In the case of endcapping experiments, the
appropriate amount of iodobenzene was added to the reaction via syringe immediately
after the solvent addition prior to heating. A second aliquot of iodobenzene was added
after 24 hours and allowed to react for 2 hours before cooling to ensure maximum
endcapping. The polymerizations were cooled and precipitated into acetone. The
polymers were extracted with hot ethanol, acetone, and acetonitrile after collection. See
Chapter 4 text for discussion on polymer drying methodologies and solubilities.
Polymer PPE-NEt2/H[51]. Reagents: DINEt (0.4532 g, 0.809 mmol), 1,4-
diethynylbenzene (41) (0.1040 g, 0.825mmol), Cul (7.7 mg, 0.040 mmol)and 47.7 mg of
Pd(PPh3)4 (0.040 mmol). 0.340 g of polymer was recovered (98% yield). Anal, caled for
C28H34N202: C, 78.10; H, 7.96; N, 6.51. Found: C, 74.30; H, 7.08; N, 6.32. The
polymer precipitated during the coarse of the reaction and was insoluble after collection
and drying.
Polymer PPE-NEt2/OC6[52]. Reagents: DINEt (0.8959 g, 1.600 mmol), 1,4-
diethynyl-2,5-bis(hexyloxy)benzene (39) (0.5321 g, 1.631 mmol), Cul (15.3 mg, 0.080
mmol) and 92.4 mg of Pd(PPh3)4 (0.080 mmol). 0.998 g of polymer was recovered (99%
yield). Anal, caled for C40H58N2O4: C, 76.15; H, 9.27; N, 4.44. Found: C, 72.10; H,


xml version 1.0 encoding UTF-8
REPORT xmlns http:www.fcla.edudlsmddaitss xmlns:xsi http:www.w3.org2001XMLSchema-instance xsi:schemaLocation http:www.fcla.edudlsmddaitssdaitssReport.xsd
INGEST IEID ER15J4GUD_MCBSAE INGEST_TIME 2013-02-14T13:43:03Z PACKAGE AA00013535_00001
AGREEMENT_INFO ACCOUNT UF PROJECT UFDC
FILES


16
in solubility and activity of the catalyst, but can undergo ligand transfer instead of the
desired aryl moiety, particularly in the case of triphenylphosphonium ligands.
Often, Stille and Suzuki polymerizations can be applied to the same desired
polymers and general guidelines should be followed in making the best choice. The
chemistry behind the synthesis of aryltin compounds used in Stille reactions involves the
use of chlorinated alkyl tin reagents which are toxic and re-generated during the course of
the reaction. Therefore, if possible the Suzuki reaction should be used. Boronic Suzuki
reagents and the salts formed during the catalytic cycle are relatively harmless. The
drawback to the Suzuki reaction is that for many electron rich aryl groups, boronic esters
or acids are much too unstable to withstand the numerous couplings needed for
polymerization. Obviously, the Heck and Sonogashira reactions are applied specifically
to the formation of vinylene and ethynylene linkages and are not alternatives to many
Suzuki or Stille routes. The reagents for each are fairly stable organics and the by
products of the catalytic cycle are mineral acids.
The palladium (0) reactions hold several advantages over other polymerization
techniques when used to make conjugated polymers. Many free radical polymerizations
convert activated double bonds to single bonds in order to achieve the couplings, while
step growth polymerizations often involve the coupling of carbon atoms to heteroatoms
with an associated release of a small molecule such as H2O. The Pd catalysts are
generally stable and tolerate most functional groups, allowing a wide range of
polymerization possibilities. Many complex repeat unit structures can be constructed by
mixing different ratios of metal and halogenated reagents. Of course, overall a
stoichiometric balance (1:1) of total halogen to metal functionality must be maintained as


3
Functionalized polymers capable of hydrogen bonding interactions can have lowered
solubility as well.
Polymers that form extended, ribbon-like structures in solution rather than a
random coil conformation are termed rigid-rod polymers. Such polymers are exemplified
by poly(/?-phenyleneterephthalamide) 1, poly(benzobisthiazole) 2, and poly(p-phenylene)
3, shown in Figure 1-1. Polymer 1 maintains its rigid-rod nature by hydrogen bonding
between chains and polymers 2 and 3 maintain the same nature by being entirely
conjugated. The conjugated polymers have the unique property of being electroactive,
meaning they have dielectric and spectral properties (such as luminescence) that depend
on applied voltages. Because of the electroactive nature of conjugated polymers, they
have become a major focus of research over the last 20 or so years. It is easy for one to
focus solely on the optical properties due to the visual nature of humans; however, it is
important not to forget mechanical property considerations, because solubility and
processing difficulties must always be dealt with in these systems.
Figure 1-1. Structures of poly(p-phenyleneterephthalamide) (1), poly(benzobisthiazole)
(2), and poly(p-phenylene) (3).
Bandgap: From Dienes to Extended Conjugation Systems
The simplest of the conjugated polymers is polyacetylene, -(CH=CH)-, which was
synthesized by Ziegler-Natta polymerization of the monomeric gas. The material is of


93
Based on the endcapped polymer repeat unit structure shown in Figure 4-15, the number
of repeat units, n, can be calculated from H NMR integration values using the formula:
4/z + 2 c 4.00
a 0.17
(4-1)
where n = 23 (46 rings) or subsequently a Mn = 16,500 g/mol. It should be noted that
this number is an approximation and several factors should be considered when using this
approximation, such as possible errors in the NMR integration values and the presence of
iodine (0.37%) in the sample, which indicates non-endcapped chain ends. Assuming a
liberal estimation of these errors, it is safe to assume that minimally a DP = 15 (Mn =
10,000 g/mol; 30 rings) has been achieved.
Figure 4-16. Expansion of the aromatic region of the H NMR of PPE-
NEt2/OC9(20)[54] in CDC13.


103
Solution absorbance of the bromoethane quatemized derivative (PPP-NEt3+[19])
in water occurred at 330 nm with corresponding photoluminescent emission at 410 nm.
The tan polymeric material could be easily manipulated into thin multi-layer LED
devices using an electrostatic adsoiption technique. Thermogravimetric analysis of the
quatemized polymer revealed an initial weight loss at 230 C due to the loss of
bromoethane and a subsequent triethylamine fragment as the side chains were cleaved
with heating under N2.
The next progression in the research was to lower the energy of the emission by
incorporation of thiophene units into the polymer backbone. Ideally, this could be
achieved using a similar Suzuki reaction as that used for the PPPs. Experimentation
revealed that use of a 2,5-thiophene diboronate ester in a Suzuki polymerization was
ineffective for the production of polymeric materials as the boronate functional groups on
thiophene are much more susceptible to hydrolysis and decomposition than those on
phenylene used for the PPP synthesis. A Stille coupling methodology was employed and
it was determined that dropwise addition of 2,5-bis(trimethylstannyl)thiophene to DINEt
in DMF with PdCl2(PPh3)2 catalyst produced the highest molecular weight polymer,PPT-
NEt2(96-drop)[28], with a Mn = 5,300 g/mol and polydispersity of 1.7. The somewhat
lower molecular weight can be attnbuted to the lower reactivity of the tin reagents used
in the Stille reaction as compared to the boronic reagents used in the Suzuki reaction and
possible methyl transfer from the 2,5-bis(trimethylstannyl)thiophene which would endcap
the polymer and terminate chain extension.
The water soluble derivative formed by treatment of the neutral polymer with
bromoethane, PPT-NEt3+(96-drop)[31], had a solution absorbance in water at 411 nm


86
C6H12OPh
Suzuki
Polymerizaton
47
Trimethyliodosilane
R
c6h12i
Et3N
R
C6H12NEt3+
\\_V~
y vJn
ACN
y vJ n
R C6H12I R C6H12NEt3+ I
48 49
Figure 4-11. Rehahns route to cationic PPPs.
o
// ^
Figure 4-12. Williamson etherification to protect bromo endgroups.
,C6H12OPh
Trimethyliodosilane
n
C6H12OPh
Figure 4-13. Envisioned application of Rehahns strategy to PPEs.


Both 'H NMR integration and elemental analysis (22.54 % Br) indicate a nearly
quantitative level of quatemization.
Neutral Polymer Syntheses
The general Suzuki polymerization is outlined in Figure 2-10. The
dialkoxyamine-dihalogenated benzene monomer, boronic reagent, Pd catalyst of choice,
and mild base such as K2CO3, Na2CC>3, or NaHCC>3 are stirred in a mixed aqueous /
organic (THF, DMF, acetone) solvent system with heating to 70 C. Special care is taken
to ensure that the reaction vessel and solvents are fully degassed with Ar prior to addition
of the catalyst and the reaction conducted under a blanket of the inert gas. Atmospheric
02 in the reaction may contribute to oxidation of the Pd catalyst and decrease its catalytic
activity and/or increase the rate of homocoupling of the boronic reagents.66
Figure 2-9. Synthesis of neutral and cationic PPP model compounds.


87
Neutral Polymer Syntheses
The general Sonagashira polymerization is outlined in Figure 4-14. DINEt, di-
ethynyl compound, Cul co-catalyst, and Pd catalyst of choice, were stirred in a solution
of toluene and amine (triethylamine or diisopropylamine) with heating to 70 C.
Temperatures above 70 C are known to promote crosslinking in the PPE chains, along
with undesired diyne defects, and were therefore avoided. When Pd(II) catalysts are
employed, the amount of di-ethynyl compound should be adjusted to account for
reduction of the catalyst to Pd(0), as shown in Figure 4-3. Pd(0) catalysts, such as
Pd(PPh3)4, are effective for the coupling and do not need to be reduced before beginning
the catalytic cycle, but careful exclusion of O2 from the reaction must be conducted. For
the polymerizations in this study, diisopropylamine and Pd(PPh3)4 were used in all
couplings.
DINEt
N
R
Polymer R
Monofunctional
Endcapping Agent
for PPE-NEt2/OC9(20)
PPE-NEt2/H[51] H
PPE-NEt2/OC6[52] OC6H13
PPE-NEt2/OC9(high) [53] OC9H19
PPE-NEt2/OC9(20) [54] OC9H19
Figure 4-14. General synthesis for alkoxy-amine containing PPEs.


5
electron. The orbitals would merge into a one-dimensional band, similar to the
conduction bands of metals. Electrons in the highest energy occupied orbitals would be
free to move into the unoccupied orbitals where they would have a high mobility. This
simple model would allow for polyacetylene to be metallic with no barrier to the free
movement of electrons in the system.
molecule
Frost's circle
relative orbital
molecular orbitals energies
orbital
type
a-2p
antibonding
a
nonbonding
a + 2P
bonding
a-2(3
a (3
antibonding
a + p
a + 2P
bonding
Figure 1-2. Application of Frosts circle to illustrate the energies of molecular orbitals
within cyclic systems.
Experiments have proven that polyacetylene is not a metallic conductor in its
neutral state. This is accounted for by analyzing the orbitals at the Fermi level. The
Fermi level is the energy level which has a 50% chance of being occupied by an electron
and represents the midpoint in energy of a symmetric half-filled band. The molecular
orbitals at the Fermi level are close enough in energy to behave as if degenerate. The
Jahn-Teller theorem5 predicts that when degenerate orbitals are unevenly filled with


95
Treatment of PPE-NEt2/OC9(20)[54] in a 50 C chloroform/acetonitrile solution
with bromoethane to synthesize PPE-NEt3+/OC9(20)[56] promoted the agglomeration
and subsequent insolubility seen in previously mentioned neutral polymer syntheses.
After 3 days of reaction time, a swollen orange material precipitated from the reaction
medium. The solution was concentrated and added to an excess of THF. An orange
material was collected via filtration, which was poorly soluble in ethanol and insoluble in
other organic solvents and water. Lowering of the pH of the ethanol solution did not
promote any extra solubility. Elemental analysis revealed a 12.58% bromine content by
weight indicating a 73% quatemization efficiency. The lowered efficiency as compared
to previously described PPP and PPT polyelectrolytes is most likely a result of the
precipitation of the polymer during the reaction and/or its strong agglomeration and
packing. The lowered number of quatemized sites cannot, in itself, account for the poor
solubility in EtOH since lowering the pH should protonate any non-quatemized sites,
thus making the polymer soluble in EtOH. The small amount of quatemized polymer
that was soluble in EtOH displayed an optical absorbance very similar to that of the PPE-
NEt2H+/OC9(20)[55] which will be discussed in detail in the Physical Properties
section. Based on these observations and results, it was determined that PPE-
NEt2H+/OC9(20)[55] could be used as an effective alternative to a bromoethane
quatemized polyelectrolyte and therefore the properties of PPE-NEt2H+/OC9(20)[55]
were investigated more fully than those of the PPE-NEt3+/OC9(20)[56] material.
Physical Properties of PPE Type Polymers
Figure 4-18 shows the UV-Vis absorbance and photoluminescence spectra for
PPE-NEt2/OC9(20)[54] in CHC13 and PPE-NEt2H+/OC9(20)[55] in low pH EtOH


63
molecular weight by GPC of all trials. Slow addition of the more reactive tin compound
allows for immediate coupling of the thiophene to DINEt. This limits the exposure of the
stannylated compound to the elevated temperatures and lowers the chance of destroying
the mass balance leading to end-capping of the polymer chains with thiophene or
completely de-stannylating the thiophene. This method led to the highest degree of
polymerization for the PPT's prepared.
ISC 143 130 1Z0 110 113 91 S3 71 It S3 41 38 21 II pp*
Figure 3-8. 'H and l3C NMR spectra of PPT-NEt2[28].


38
Table 2-3. Effect of DBNEt or DINEt on the molecular weight of PPP-NEt2 polymers.
polymer
reaction
solvent
reaction
type
reaction
time
(hours)
K
MP
K
MjMn
PPP-NEt2
(Br-72)[14]
dmf/h2o
Suzuki
72
15.9
24.3
35.0
2.20
PPP-NEt2
(I-3)[15]
DMF/H20
Suzuki
3
10.9
13.3
16.6
1.52
PPP-NEt2
(I-24)[16]
DMF/H2O
Suzuki
24
15.3
19.5
27.5
1.80
Molecular weight values are expressed in units of kg mol1.
GPC relative to polystyrene standards.
Figure 2-13. Envisioned boronic reagents for a more substituted PPP-NEt2 polymer.
Pd(OAc)2
DMF, heat
Figure 2-14. Pd catalyzed coupling to diboronic reagents for Suzuki couplings.


69
100 -
80-
Co' 60-
20-
0-
0
i 1 1 1 1 1 < 1 1 1 1 r~
100 200 300 400 500 600 700 800
Temperature (C)
Figure 3-12. TGA thermograms for neutral and water soluble PPT-NEt under N2.
a) PPT-NEt2[28]
b) - PPT-NEt3+[31]
Conclusions
A water soluble poly(/?-phenylene-co-thiophene) (PPT-NEt3+[31]) has been
synthesized by a variety of modifications of Stille polymerization techniques. Maximum
molecular weight was achieved in DMF using PdCl2(PPh3)2 catalyst with slow addition
of the 2,5-bis(trimethylstannyl)thiophene reagent. Again, as in the case of the PPP-NEt2
system, the polymer does begin to precipitate from the reaction over the coarse of the
reaction, limiting the molecular weights. Polymerizations attempted in THF as solvent
did not produce polymeric materials. Unfortunately, the use of PPT-NEt3+[31] in
electroluminescent devices appears unlikely due to low light emission in such devices.
However, preliminary work has shown that the material may hold promise in
electrostatically deposited thin layer systems for control over refractive index properties.


127
1.4-diethynyl-2,5-bis(hexyloxy)benzene (39). Reagents: 1,4-
bis((trimethysilyl)ethynyl)-2,5-bis(hexyloxy)benzene (1.91 g, 4.1 mmol). Solvent was
removed to give a yellow crude material which was passed through a silica gel column
(1:1 hexanes/CH2Cl2) and crystallized from hexane resulting in collection of 1.25 g of a
light yellow material (94 % yield). H NMR (300 MHz, CDC13) 6.95 (s, 2 H), 3.97 (t, 4
H), 3.34 (s, 2H), 1.80 (m, 4 H), 1.34-1.47 (m, 12 H), 0.90 (t, 6 H) ppm. '3C NMR (75
MHz,CDC13) 154.03, 117.33, 114.04, 101.09, 100.02, 69.52,31.61,29.32, 25.70, 22.63,
14.05 ppm. Anal. Caled for C22H30O2: C, 80.93 ; H, 9.27. Found: C, 81.20; H, 9.15.
FAB-HRMS (M)+calculated for C22H30O2: 326.2246, Found 326.2240.
1.4-diethynyl-2,5-bis(nonyloxy)benzene (40). Reagents: 1,4-
bis((trimethysilyl)ethynyl)-2,5-bis(nonyloxy)benzene (1.52 g, 2.7 mmol). After
extractions, solvent was removed to give a crude yellow material which was crystallized
from hexane to give 1.06 g of a light yellow material (95 % yield). H NMR (300 MHz,
CDC13) 6.95 (s, 2 H), 3.97 (t, 4 H), 3.33 (s, 2 H), 1.80 (m, 4 H), 1.20-1.60 (m, 24 H),
0.88 (t, 6 H) ppm. ''C NMR (75 MHz, CDC13) 153.97, 117.76, 113.27, 82.36, 79.77,
69.66, 31.86, 29.49, 29.30, 29.21, 29.11, 25.87, 22.65, 14.07 ppm. Anal. Caled for
C28H42O2: C, 81.89; H, 10.32. Found: C, 82.02; H, 10.68. FAB-HRMS (M)+calculated
forC28H4202: 410.3185, Found 410.3183.
Compounds 43-45. See reference 54c for complete synthetic details.
2.5-Bis(6-bromohexyl)-l,4-diiodobenzene (46). A 250 mL, 3 neck round
bottom flask was charged with compound 45 (2.11 g, 5.22 mmol) and a solvent system
consisting of 90:7:3 HOAc/ H2O/ H2SC>4by volume. CHCI3 was added until compound
45 was dissolved. 12 (1.63 g, 6.27 mmol) and KI04 (1.44 g, 6.27 mmol) were added and


Q
,0
NaCN
,0 Q
H
NaCN
Lawesson's
(00;
x Br'^\S/^Br + y Br^ ^
Br
1. Mg
2. Ni(acac)2
xmu
R
2eq. + Br
Pd(0)
M = ZnCI, SnMe3
R = H, alkyl, alkoxy, functional group
R
ClZn o _
ZnCI R
R = alkyl, alkoxy, nitro
Figure 3-1. Literature examples of phenylene-co-thiophene type polymers.
Pd(0)
XRX + Bu3SnR'-SnBu3
-(H-n
X = I, Br, 0S02CF3i COCI
R, R' = aromatic, vinyl, heterocyclic, etc.
Figure 3-2. General scheme for the Stille polymerization.


k
T . 1 1 1 1 1 r- i 1 1 1 1 1 i rr
7 6 S 4 3 Z
13C NMR Peaks
153.44
117.09
77.53
69.59
68 24
51.58
47.94
31.88
29.69
29.61
29.41
29.30
25.93
22 67
14.11
12.16
160 140 120 100 80
40 20
ppm
Figure 4-15. 'H and 13C NMR of PPE-NEt2/OC9(20)[54] in CDC13.


131
117.09, 77.93, 69.59, 68.24, 51.58, 47.94, 31.88, 29.69, 29.61, 29.41, 29.30, 25.93, 22.67,
14.11, 12.16 ppm Anal, caled for C46H7oN204: C, 77.27; H, 9.87; N, 3.92. Found: C,
75.66; H, 9.64; N, 3.41; I, 0.37. UV-Vis (CHC13) Amax = 442 nm, log rmax = 4.63. UV-
Vis (1M HC1 in EtOH, PPE-NEt2H+/OC9(20)[55]) max = 408 nm, log £-max = 5.04.
PL (CHCb) Amax = 502 nm; Quantum Yield = 0.001. PL (1M HC1 in EtOH, PPE-
NEt2H+/OC9(20)[55]) Amax = 464 nm; Quantum Yield = 0.86. Mn{\ia 'H NMR) =
16,500 g/mol.
Polymer PPE-NEt3+/OC9(20)[56]. PPE-NEt2/OC9(20)[54] (0.173 g, 0.24
mmol) was dissolved in 50 ml of CHCI3 and an excess of bromoethane was added (10
mL). The reaction was heated to 50C and stirred for 3 days. Each day ~10 mL of
acetonitrile was added to ensure that the polyelectrolyte being formed remained in
solution. Over the coarse of the reaction, a swollen orange material did precipitate from
the reaction. The reaction was cooled, concentrated, and added to 200 mL of THF. 200
mg of an orange solid was recovered (88% yield). The material was poorly soluble in
ethanol and insoluble in water, chloroform, and THF. The portion of material soluble in
ethanol displayed optical absorbances similar to that of PPE-NEt2H+/OC9(20)[55].
Anal, caled for C5oH8oN204Br2: C, 64.37; H, 8.64; N, 3.00; Br. 17.13. Found: C, 66.06;
H, 8.92; N, 3.03; Br, 12.58.


27
matter of filtration. The reactions lower yield is probably a result of some DBHQ
remaining dissolved in the solvent. No attempts were made to recover this lost
material. Recrystallization of the slightly pink crude product from a hot 4:1 (v/v) water
to isopropanol solvent solution removed the undesired impurities.
OH
2.1 eq. Br2
MeCIo / AcOH
HO 6
DBHQ
40%
Figure 2-6. Bromination of hydroquinone in the 2,5 positions.
DIHQ and DBHQ were subjected to Williamson etherification conditions in
refluxing acetone with 2.1 equivalents of 2-chlorotriethylamine hydrochloride (7) and 4.0
equivalents of K2CO3 for three days, as outlined in Figure 2-7, to produce the desired 1,4-
dihalo-2,5-dialkoxyamine phenylene monomers, DINEt and DBNEt. Four equivalents
of K2CO3 were necessary for deprotonation of the hydroquinone and the hydrochloride
salt of the 2-chlorotriethylamine reagent which was deprotonated in situ. Isolation of the
organic chlorinated amine would be difficult as cyclization to the aziridinium ion would
likely occur. Grinding of the K2CO3 by mortar and pestle, followed by drying in an oven
overnight, generally increased yields by 10%. The monomers were isolated and
recrystallized twice from methanol / water to achieve maximum purity and dried over
CaSQ* under vacuum to ensure dryness for the accurate mass measurements necessary
for step growth polymerizations. DBNEt was recovered in lower yield due to larger
amounts of material being lost during the recrystallization steps.


34
PdCI2(dppe) PdCI2(dppp) PdCI2(dppf)
Cl-Pd-Cl Bond Angle 94.2 90.8 87.8
Figure 2-11. Cl-Pd-Cl bond angle for PdCl2(dppe), PdCl2(dppp), and PdCl2(dppf)
catalysts.
MeOH after 3 hours. GPC results in chloroform (vs. PS standards) revealed low
molecular weight oligomers (Mn < 1,500 g mol'1, multi-modal) for the reaction
usingthe dibromonated species [PPP-NEt2(Br-3)]. The reaction using the diiodonated
reagent [PPP-NEt2(I-3)[15]] reached a Mn = 10,900 g mol'1 with a continuous
polymeric distribution. Published results using DBNEt in the reaction for 72 hours
showed a Mn = 15,900 g mol1 for the resulting polymer [PPP-NEt2(Br-72)[14]]. The
elemental analysis and GPC results are summarized in Tables 2-2 and 2-3, respectively.
Longer reaction times (complete polymerization stopped after 24 hours) with DINEt
[PPP-NEt2 (I-24)[16] ; Mn = 15,300 g mol'1 ] approached the molecular weight values
reported for PPP- NEt2(Br-72)[14], The use of DINEt leads to the formation of a
polymer with similar molecular weight properties to PPP-NEt2(Br-72)[14] in a shorter
amount of time. Once the polymer has reached a certain molecular weight, it begins to
precipitate out of solution, stopping polymer growth, and negating the advantages of the
more reactive iodine reagent at longer reaction times.


10
soliton states form bonding and antibonding combinations, producing two gap states
symmetrically displaced about the midgap (see Figure 1-5). The levels can be occupied
by 0 to 4 electrons giving a positive bipolaron (bp2+), positive polaron (p+), polaron
exciton, negative polaron (p'), or negative bipolaron (bp2 ).
ground state excited state

exciton
Figure 1-4. Geometrical relaxation of a PPV chain in response to photo- or electo-
excitation.
rc conduction band
luminescence
t
bp2+ p+ polaron- P bp2
n valence band exciton
Figure 1-5. Polaron, bipolaron, and singlet exciton energy levels in a non-degenerate
ground-state polymer.
Singlet and triplet excitons have been shown to exist in conjugated polymers.
Taking into account both Coulonbic and electron-lattice interactions, the triplet exciton
and singlet exciton are no longer of the same energy nor of the same size. The triplet
exciton becomes more localized than the singlet exciton which may extend over several


53
Number average molecular weights of up to 22,000 g mol'1 were achieved for the
PPT polymers using 1.00 equivalent of l,4-diiodo-2,5-dioctylbenzene, 1.02 equivalents
of 2,5-bis(tributylstannyl)thiophene, and 2 mol% PdCl2(PPh3)2 catalyst in 80 C DMF for
one week. Of all organotin monomers studied, the 2,5-bis(tributylstannyl)thiophene (see
Table 3-2) was the most reactive, as the electron donating property of the sulfur atom
may accelerate the transmetalation step which has been proposed to be the rate
80
determining step for palladium-catalyzed cross coupling reactions. An alternate tin
reagent not used in Yus study is 2,5-bis(trimethylstannyl)thiophene, which is a more
friendly reagent in that it is a solid at room temperature allowing for purification by
recrystallization. The distillation techniques needed to purify 2,5-
bis(tributylstannyl)thiophene are difficult and workers may be exposed to alkyltin vapors,
which are very toxic. One drawback to the use of 2,5-bis(trimethylstannyl)thiophene is
the transfer of a methyl group during coupling instead of the desired thiophene group and
limiting chain lengths in polymerizations.
This methodology appeared attractive for coupling distannylated thiophene with
2,5-bis(3-[7V,iV-diethylamino]-l-oxapropyl)-l,4-diiodobenzene (DINEt)[see Chapter 2].
If successful, a neutral poly(/?-phenylene-c<9-thiophene) with alkoxyamine side chains on
the phenylene units would be created that should become water soluble upon treatment
with ethyl bromide. The solution emission of this polymer should fall in the green to
yellow visible wavelength range by comparison to literature values. Using the insights
into the Stille coupling found by Yu and coworkers, and taking into account the specific
differences between the proposed system and the literature examples, a systematic
approach was designed to maximize the molecular weight of poly({2,5-bis[2-(iV,A-


43
Wavelength
Figure 2-16. UV-Vis / Emission behavior of neutral and water soluble PPP-NEt.
a) PPP-NEt2[12] in THF: plots c and f
b) PPP-NEt2[12] in 1 M HC1: plots b and d
c) PPP-NEt3+[19] in H20: plots a and e
Figure taken from Balanda, P.B.; Ramey, M.B.; Reynolds, J.R.
Mcicromolecules 1999, 32, 3970.
Thermal analysis by TGA (under nitrogen atmosphere) (Figure 2-18) indicated an
onset for decomposition over 300C for PPP-NEt2[12] and at ca. 230C for PPP-
NEt3+[19] (with a small amount of water loss at lower temperatures). From the
perspective of device applications, the most important degradation event is the one which
occurs first. The first degradation event for both polymers was determined to be side
chain cleavage, including the loss of ethyl bromide for the quatemized sample. The
PL Intensity ( a.u.)


8
those most responsible for the early work, Alan J. Heeger, Alan G. MacDiarmid, and
Hideki Shirakawa. The door for a myriad of creative syntheses to incorporate aromatic
hydrocarbons, heterocycles, vinyl, and ethynyl groups into the backbone of 7i-conjugated
polymers was opened by the initial work on polyacetylene. Important properties not
envisioned with the discovery of polyacetylene, such as electrochromism and
electroluminescence, have evolved with these newer materials. The properties and
syntheses of these materials are much too varied and exciting to sufficiently cover in this
dissertation, but an excellent starting reference for investigating these materials is The
Handbook of Conducting Polymers.11 Focus will be placed, herein, on the property of
electro/photo-luminescence and the synthetic application of palladium (0) catalyzed
coupling reactions to the preparation of conjugated polymers.
Luminescence: Photo- and Electro-
Much of the discussion and graphical representations presented in this
introduction to the electroluminescence of conjugated polymers is based on the review of
the topic by Richard H. Friend and Neil C. Greenham in Electroluminescence in
Conjugated Polymer in The Handbook of Conducting Polymers (see Ref. 11). Please
refer to this reference for a more complete discussion of the technical specifics for
construction and properties of light emitting diodes (LEDs).
Electroluminescence is the generation of light by electrical excitation and was
first reported for an organic semiconductor in 1963 by the observed emission of light
from single crystals of anthracene.12 Studies on these simple electroluminescent organic
semiconductors established that the process responsible for the emission of light requires
the injection of electrons from one electrode and holes from the other, the capture of one


CHAPTER 5
CONCLUSIONS
Polymer chemistry and science, once thought of as merely a grafted branch onto
the tree of traditional chemistries (organic, inorganic, physical), has taken its place as a
fundamental science over the past decades. The tree of polymer chemistry will always
be rooted in the above mentioned chemical divisions, but it has grown to unexpected
heights on its own merits and branched into fields of study hitherto unforeseen. It is
fitting that many of todays most advanced research efforts are now using polymer
science as the foundation of growth, while trying to add traditional chemical and
biochemical functionalities to the macromolecular design. As control over
supramolecular shapes and folding, like that seen in proteins, advances one can only
imagine the structure/property relationships that will become available during the next
decades.
One of the largest fields of current study is in the field of electroactive polymers,
which display remarkable optical and conductive properties when potentials are applied.
The focus of this dissertation is to shed light on the synthesis, stability, and basic optical
properties of a series of conjugated polyelectrolytes. These unique conjugated polymers
not only have interesting optical properties, but are of interest in basic polymer science
for the study of the effects of the rigid backbone versus that of the pendant side chain
charges on the polymer shape (polyelectrolyte effect). Using Suzuki, Stille, and
Sonogashira type Pd(0) cross-coupling reactions, a series of three different polymer
101


46
Increasing the number of unsubstituted phenyl rings in the polymer backbone,
PPPBP-NEt2[13], lowers molecular weight due to precipitation of the polymer out of the
reaction prior to high conversions. Subsequent optical absorption data on thin film
castings of less substituted samples to the more substituted PPP-NEt2[12] helps support
the theory that the alkoxyamine side groups on PPP-NEt2[12] have minimal interactions
that affect backbone planarity.


102
backbones were synthesized [poly(p-phenylene), poly(/?-pheneylene-cc>-thiophene), and
poly(/?-pheneyleneethynylene)], each with its own distinguishing physical, chemical, and
optical properties.
Chapter 2 of this dissertation presents the experimental work on the poly(p-
phenylene) derivatives (PPP-NE2) which contain alkoxy-amine side chains that can be
quatemized or protonated to generate water soluble polymers that emit blue light. Initial
work conducted by Dr. Peter Balanda was expanded upon to allow for scale up
production and elimination of contamination by precipitated Pd(0) metal into the
polymer. Modified Suzuki polymerization protocols were employed in the various PPP-
NEt2 syntheses to couple bis(neopentylglycol)-l,4-phenylenediboronate with 2,5-bis(3-
[N,iV-diethylamino]-l-oxapropyl)-l,4-diiodobenzene (DINEt). The use of PdCPCdppf)
catalyst was a success in achieving the desired goals as a polymer, PPP-NEt2(dppf)[12],
of Mn = 18,700 g/mol and polydispersity of 1.18 based on GPC results versus
polystyrene standards was recovered from multi-gram scale reactions without
contamination from black Pd(0).
Several key synthetic insights were also gained from the work concerning the
nature of the halogenated monomer and solvent choice. Iodinated monomers were found
to react the fastest, but ultimate polymer molecular weights were very similar to
polymerizations conducted with brominated monomers. This result is due to the
precipitation of the polymer during the coarse of reaction, thereby terminating chain
growth based on solubility limits. The polar solvents THF and DMF with added water
were the most effective solvents compared to acetone, methanol, or toluene.


138
86. (a) Tateishi, M.; Nishihara, H.; Aramaki, K. Chem. Lett., 1987, 1727. (b)
Kahata, T.; Oosawa, T. JP-Patent 63 205,052 [88 205,052]; Chem. Abstr., 1989,
110, 26700.
87. Schopov, I.; Vodenicharova, M. Makromol. Chem., 1978, 179, 63.
88. Agrawal, A.K.; Jenekhe, S.A. Chem. Mater., 1992,4,95.
89. (a) Dieck, H.A.; Heck, R.F. J. Organomet. Chem. 1975, 93, 259. (b) Cassar, I.
J. Organomet. Chem. 1975, 93, 253. (c) Sonogashira, K.; Tohda, Y.; Hagihara,
N. Tetrahedron Lett. 1975, 16, 4467.
90. Osakada, K.; Sakata, R.; Yamamoto, T. Organometallics 1997,16, 5354.
91. Giesa, R.; Schulz, R.C. Macromol. Chem. Phys. 1993, 191, 857.
92. Moroni, M.; LeMoigne, J.; Luzzati, S. Macromolecules 1994, 27, 562.
93. (a) Ofer, D.; Swager, T.M.; Wrighton, M.S. Chem. Mater. 1995, 7, 418. (b)
Swager, T.M.; Gil, C.J.; Wrighton, M.S. J. Phys. Chem. 1995, 99, 4886.
94. (a) Weder, C.; Wrighton, M.S. Macromolecules 1996, 29, 5157. (b) Weder, C.;
Wrighton, M.S.; Spreiter, R.; Bosshard, C.; Giinter, P. J. Phys. Chem. 1996,100,
18931.
95. Steiger, D.; Smith, P.; Weder, C. Macromol. Rapid Commun. 1997, 18, 643.
96. Kim, J.S.; McHugh, S.K.; Swager, T.M. Macromolecules 1999, 32, 1500.
97. Li, H.; Powell, D.R.; Hayashi, R.K.; West, R. Macromolecules 1998, 31, 52.
98. Yang, J.S.; Swager, T.M. J. Am. Chem. Soc. 1998,729,5321.
99. Zhou, Q.; Swager, T.M. J. Am. Chem. Soc. 1995, 777, 12593.
100. Francke, V.; Mangel, T.; Mllen, K. Macromolecules 1998, 31, 2447.
101. a) Giesa, R. J.M.S.-Rev. Macromol. Chem. Phys. 1996, 36, 631. (a) Bunz,
U.H.F. Chem. Rev. 2000, 100, 1605.
102. (a) Ley, K.D.; Whittle, C.E.; Bartberger, M.D.; Schanze, K.S. J. Amer. Chem.
Soc. 1997,119, 3423. (b) Walters, K.A.; Ley, K.D.; Schanze, K.S. J. Chem.
Soc., Chem. Commun. 1998, 10, 1115. (c) Ley, K.D.; Schanze, K.S.
Coordination Chem. Rev. 1998, 777, 287. (d) Ley, K.D.; Walters, K.A.;
Schanze, K.S. Synthetic Metals. 1999, 102, 1585. (e) Ley, K.D.; Li, Y.T.;
Johnson, J.V.; Powell, D.H.; Schanze, K.S. J. Chem. Soc., Chem. Commun.
1999, 77, 1749.
103. Johnstone, R.A.W.; Rose, M.E. Tetrahedron 1979, 35, 2169.


4-4. Synthesis of dialkoxy poly(p-phenyleneethynylene)s via the Sonogashira reaction.. 75
4-5. Representative structures of synthetic modifications to poly(/?-
phenyleneethynylene)s 77
4-6. Williamson etherification to synthesize various 1,4-dialkoxyphenylenes 78
4-7. Iodination of various 1,4-dialkoxybenzenes 79
4-8. Synthesis of various 1,4-diethynylphenylene monomers 80
4-9. Synthesis of 2,5-bis(6-bromohexyl)-l,4-diiodobenzene 83
4-10. Gas chromatography analysis of purification of 6-bromohexylmethylether (43) by
vacuum distillation using (a) simple vigreux column and (b) spinning band
column 85
4-11. Rehahns route to cationic PPPs 86
4-12. Williamson etherification to protect bromo endgroups 86
4-13. Envisioned application of Rehahns strategy to PPEs 86
4-14. General synthesis for alkoxy-amine containing PPEs 87
4-15. H and 13C NMR of PPE-NEt2/OC9(20)[54] in CDC13 92
4-16. Expansion of the aromatic region of the H NMR of PPE-NEt2/OC9(20)[54] in
CDC13 93
4-17. Conversion of PPE-NEt2/OC9(20)[54] to cationic polyelectrolytes 94
4-18. Normalized UV-Vis absorption and solution photoluminescence for PPE-OC9(20)
type polymers 97
4-19. TGA thermograms for neutral and protonated PPE-OC9(20) under N2 98
x


114
PPP-NE2(I-3)[15]. Reagents: DINEt (1.0189 g, 1.819 mmol),
bisneopentylglycol-l,4-phenylene diboronate (8, 0.5492 g, 1.819 mmol), Na2C3 (1.93 g,
18.21 mmol), and Pd(OAc)2 (6.73 mg, 0.03 mmol) 25 mL DMF and 5 mL H2O were
used as solvent. Reaction time: 3 hours. Yield: 0.50 g [72 %]. Anal, caled for
C24H34N2O2I0.045: C, 74.24; H, 8.42; N, 7.22; I, 1.47. Found: C, 67.32; H, 8.42; N, 6.01;
I, 1.48. GPC (CHCI3 vs. PS) Mn = 10,900 g mol1, MP = 13,300 g mol1, Mw = 16,600
g mol1, Mw/Mn = 1.52.
PPP-NE2 (I-24)[16]. Reagents: DINEt (0.9589 g, 1.712 mmol),
bisneopentylglycol-l,4-phenylene diboronate (8, 0.5169g, 1.712 mmol), Na2C03 (1.8lg,
17.12 mmol), and Pd(OAc)2 (6.73 mg, 0.03 mmol) 25 mL DMF and 5 mL H2O were
used as solvent. Reaction time: 24 hours. Yield: 0.52 g [80%]. Anal, caled for
C24H34N2O2I0.023: C, 74.82; H, 8.83; N, 7.27; 1,0.76. Found: C, 71.85; H, 8.45; N, 6.78;
I, 0.77. GPC (CHCI3 vs. PS) Mn = 15,300 g mol'1, MP = 19,500 g mol'1, Mw = 27,500
g mol'1, Mw/Mn =1.80.
Polyi^S-bis^-iA^N-diethylaminoFl-oxapropyll-l^-phenyleneJ-a/M^-
biphenylene) [PPPBP-NEt2[13]]. 50 mL of THF and 10 mL of H2O were sparged with
argon under reflux for 1 hour. A 200 mL Schlenk flask with a magnetic spin bar was
charged with DBNEt (0.5975 g, 1.28 mmol), bisneopentylglycol 4,4-
diphenylenediboronate (9, 0.4848 g, 1.28 mmol), NaHCC>3 (1.07 g, 12.74 mmol), and
PdCl2(dppf) (10 mg, 1 mol %) [Strem Chemicals Inc.]. The flask was evacuated and
backfilled with argon three times. The THF/FLO solvent solution was added via cannula
to the flask and the reaction was heated to 75C and stirred for 3 days. The solution was
precipitated into 200 mL of cold methanol and collected on a glass frit. The polymer was


62
Table 3-5. Elemental Analysis results for PPT monomers and polymers.
Species
%C
%H
%N
%I
%Br
Anal. Caled, for
Compound
Theo.
29.32
4.92
-
-
-
CioH2iSSn2
21
Exp.
29.65
4.60
-
-
-
Compound
Theo.
54.52
7.20
-
-
-
c,4h2204b2s
23
Exp.
54.70
7.14
-
-
-
PPT-NEt2
Theo.
66.33
8.04
7.03
2.52
-
C22H32N2O2SI0.079
(48)[25]
Exp.
65.23
7.84
6.65
2.50
-
PPT-NEt2
Theo.
67.13
8.14
7.12
1.19
-
C22H32N2O2SI0.037
(96)[26]
Exp.
63.64
8.03
6.46
1.20
-
PPT-NEt2
Theo.
67.13
8.14
7.12
1.19
-
C22H32N202SIo.o37
(240)[27]
Exp.
63.99
7.99
6.60
1.22
-
PPT-NEt2
Theo.
67.38
8.17
7.15
0.97
-
C22H32N202SIo.o3o
(96-drop)[28]
Exp.
63.99
8.02
6.51
0.98
-
Theo.
51.09
6.88
4.58
0.77
26.20
C22H32N202SIo.o37
PPT-NEt3+
(96)[30]
' 2.0 C2H5Br
Exp.
49.87
6.48
3.18
-
24.18
PPT-NEt3+
Theo.
51.16
6.89
4.59
0.62
26.24
C22H32N202SIo.o30
2.0 C2H5Br
(96-drop)[31]
49.73
6.52
3.29
23.62
Exp.
-
PPT-NEt2
Theo.
68.04
8.23
7.23
-
-
c22h32n2o2s
(Suz)[29]
Exp.
64.70
7.98
6.60
0.09
-
produced a polymer with the lowest percent of halogentated endgroups(weight %I = 0.98;
approximates a degree of polymerization = 27, corresponding to 54 rings) and highest


2
the buildup of repeat units and properties within conjugated polymer systems (materials
with alternating single and double/triple bonds). These polymers have exciting new
applications for optical display markets, which could never have been envisioned during
the early days of the science.
Background and Theory of Conjugated Polymers
One of the simplest organic molecules is the two carbon molecule ethene,
CH2CH2, which exists as a gas under standard temperature and pressure. Polymerization
of the molecule leads to long chains of covalently bound two carbon units, -(CH2CH2)-,
termed polyethylene. As the number of covalent bonds increases, the material moves
through liquid (20 repeats), waxy (100 repeats), brittle plastic (200 repeats), and tough
plastic (>200-300 repeats) stages of mechanical properties. In the 100-200 repeat unit
regime as chain lengths become long enough to entangle, a material with plastic qualities
emerges that bridges the gap between crystallites to form tougher materials.
Most polymers have a minimum molecular weight threshold where mechanical
properties do not change greatly with additional coupling. Higher molecular weights
may produce polymers that are more difficult to process due to poor solubility or very
high melting temperatures. A balance must be achieved for each particular polymer
system to make good materials that can be molded for use. As more complicated
polymer systems are envisioned, several factors control the molecular weight to solubility
ratio. Side chain branching from the backbone of linear polymers reduces ordering and
lowers the degree of crystallinity and has become a standard method of increasing
polymer solubility. Incorporation of unsaturated bonds or aromatic rings in the backbone
reduces rotational freedom of the polymer chain, thereby stiffening the chain.