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Photophysical studies of pi-conjugated oligomers and polymers that incorporate inorganic MLCT chromophores

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Title:
Photophysical studies of pi-conjugated oligomers and polymers that incorporate inorganic MLCT chromophores
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Walters, Keith A., 1975-
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English
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xvii, 252 leaves : ill. ; 29 cm.

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Subjects / Keywords:
Absorption spectra ( jstor )
Chromophores ( jstor )
Emission spectra ( jstor )
Fluorescence ( jstor )
Lasers ( jstor )
Low temperature ( jstor )
Oligomers ( jstor )
Phosphorescence ( jstor )
Polymers ( jstor )
Rhenium ( jstor )
Chemistry thesis, Ph.D ( lcsh )
Dissertations, Academic -- Chemistry -- UF ( lcsh )
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bibliography ( marcgt )
theses ( marcgt )
non-fiction ( marcgt )

Notes

Thesis:
Thesis (Ph.D.)--University of Florida, 2000.
Bibliography:
Includes bibliographical references (leaves 235-250).
General Note:
Printout.
General Note:
Vita.
Statement of Responsibility:
by Keith A. Walters.

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University of Florida
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University of Florida
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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.
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PHOTOPHYSICAL STUDIES OF PI-CONJUGATED OLIGOMERS AND
POLYMERS THAT INCORPORATE INORGANIC MLCT CHROMOPHORES














By

KEITH A. WALTERS


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

UNIVERSITY OF FLORIDA


2000






























To the brave warrior in all of us...














ACKNOWLEDGMENTS


When you reach this point in your academic career, it is hard to go through and

thank all the individual people who guided you along the long path. First, I must thank

my parents for giving me the freedom to explore the wonderful world of life without

having the script already written for me. I also appreciated their patience when I opted

out of my initial career choice (medical school), decided to journey to Florida for

graduate school, and became a Methodist!

My desires to be a teacher (aside from the teaching experiences of my own

parents) come from two people. David Stamey, a history teacher in high school, made the

comment to me one day that I had better be a teacher or he would "hunt me down." At

the time I had problems understanding this compliment, but I can definitely tell Mr.

Stamey to put his gun away! The initial desire to teach was planted in his classes, but it

took my own experiences as a teaching assistant at Furman to spawn its full fruition. My

undergraduate advisor, mentor, and friend, Dr. Noel A.P. "crazy Australian"

Kane-Maguire, had a big hand in opening my eyes (color blind as they are) to the world

of photochemistry. Indeed, the entire chemistry department at Furman should be thanked

for their willingness to educate with the intensity and zeal they presented day after day.

I am firmly convinced that a student's experience in graduate school largely rests

in the hands of his or her graduate advisor. I am thankful to have been blessed with an

advisor that made it an amazing experience, Dr. Kirk Schanze. Kirk was always willing








to treat me as a colleague rather than a subordinate, and that works wonders on one's

creativity and initiative. I always appreciated his words of encouragement, his unique

ideas to try next, and his patience to let me try some things that probably would have

never worked out no matter what I did. Kirk gave me the freedom to learn and grow as

my own mind evolved, and that is probably the best gift any advisor can give.

Many people in Gainesville have made it a very good home for me. My fellow

group members (Joanne, Benjamin, Ed, Carla, Kevin, Yiting, Ben, Brian, Wang, Hai-

Feng) are all wonderful collaborators, willing to discuss problems and able to synthesize

those darned compounds that elude me! I look forward to seeing each and every one of

them prosper in their own professional and personal lives. The collaborations within the

department (especially with Dr. Dan Talham and Dr. Aiping Wu for the LB film work)

are always top notch. Outside of UF, my handbell choir at Trinity (Kathy, Keith [the

other one!], Andrew, Mark and Kristen, Quenta and Dana, Connie, Judy, Susan, Cheryl,

Dori, Nick, Jackie, Anna, Neil, and Rose) always brought a smile to my face, put a song

in my heart, and reminded me that other things do go on outside of a chemistry lab.

I have many collaborators outside of UF that have expanded the girth of my

understanding and appreciation of the world of chemistry. These include Dr. Stephan

Guillerez and Lise Trouillet at CEA-Grenoble, Dr. Hans van Willigen and Dr. Alejandro

Bussandri at the University of Massachusetts at Boston, Dr. Linda Peteanu and Lavanya

Premvardhan at Carnegie Mellon University, and Dr. Robert Pilato and Dr. Kelly Van

Houten at the University of Maryland.








Lastly, I thank God for giving me the gifts to do what I do and the initiative to

actually use the gifts once I discover them. With His blessing, I pray that my life will

continue to grow and prosper both inside and outside of the chemistry lab.














TABLE OF CONTENTS
page

A CKN OW LEDGM EN TS ................................................................................................. iii

LIST O F TABLES ............................................................................................................. ix

LIST OF FIGU RES............................................................................................................ xi

ABSTRA CT..................................................................................................................... xvi

7t-CON JU GA TED POLYM ERS ......................................................................................... 1

Introduction.................................................................................................................... 1
Phenylenevinylene- and Aryleneethynylene-Based Polymers................................. 1
Polythiophene-Based Polym ers ............................................................................... 7
M LCT-Incorporated nt-Conjugated Polym ers.............................................................. 12
Phenylenevinylene- and Aryleneethynylene-Based Polymers ............................... 12
Polythiophene-Based Polym ers ............................................................................. 18
Previous Group W ork.................................................................................................. 20
Scope of This W ork..................................................................................................... 22

PH OTOTHERM A L CHEM ISTRY ................................................................................... 24

Theory ..........................................................................................................................25
Tim e-Resolved Therm al Lensing........................................................................... 25
The therm al lens theory.................................................................................... 26
A sim plified calculation m ethod...................................................................... 29
Lim stations and instrum ental considerations ................................................... 32
Photoacoustic/Laser-Induced Optoacoustic Spectroscopy..................................... 35
Early photoacoustic techniques........................................................................ 37
Laser-induced optoacoustic spectroscopy........................................................ 38
A accounting for solution volum e changes......................................................... 41
Instrum ent Design and Calibration Studies ................................................................. 43
Tim e-Resolved Therm al Lensing........................................................................... 43
Apparatus setup................................................................................................ 43
Calibration studies ........................................................................................... 45
Laser-Induced Optoacoustic Spectroscopy............................................................ 48
Apparatus setup................................................................................................ 48
Calibration study (b)Rel(CO)3(bzpy)+ triplet energies.................................. 50
Experim ental.............................................................................................................. .. 60









(b)Re'(CO)3(bzpy) Synthesis................................................................................ 60
(b)Re(CO)3(bzpy)+ Photophysics........................................................................... 63

5-5' BIPHENYL OLIGOMER PHOTOPHYSICS ............................................................ 65

Introduction.................................................................................................................. 65
Results.......................................................................................................................... 65
Absorption Spectra................................................................................................. 67
Em mission Spectra.................................................................................................... 70
Em mission Lifetim es ................................................................................................ 80
Transient Absorption Spectra ................................................................................ 84
Phototherm al M easurem ents.................................................................................. 89
Transient Absorption Quenching / Oligomer Triplet Energy ................................ 91
Decay Rate Calculations........................................................................................ 93
Excited-State Energy Transfer............................................................................... 96
Langm uir-Blodgett Film s....................................................................................... 98
Electrochem istry .................................................................................................. 106
D iscussion.................................................................................................................. 106
O ligom er Ligand Conform ation........................................................................... 106
Electronic absorption spectra......................................................................... 108
Em mission spectra............................................................................................ 109
O ligom er triplet energies ............................................................................... 110
Oligomer Temperature Dependence and Aggregation......................................... 111
Excited State Photophysics of the Rhenium Complexes..................................... 115
Experim ental.............................................................................................................. 122
Oligom er and Com plex Synthesis........................................................................ 122
Photophysical M easurem ents............................................................................... 123
Electrochem ical M easurem ents........................................................................... 124
Langm uir-Blodgett Film Preparation................................................................... 125

5-5'MONOPHENYL OLIGOMER PHOTOPHYSICS.................................................. 126

Introduction................................................................................................................ 126
Results........................................................................................................................126
Absorption Spectra............................................................................................... 128
Em mission Spectra.................................................................................................. 129
Em mission Lifetim es .............................................................................................. 135
Transient Absorption Spectra .............................................................................. 138
Electrochem istry .................................................................................................. 140
D iscussion.................................................................................................................. 140
Experim ental.............................................................................................................. 145
Oligom er and Com plex Synthesis........................................................................ 145
Photophysical M easurem ents............................................................................... 146
Electrochem ical M easurem ents........................................................................... 146









4,4' OLIGOM ER PH OTOPHY SICS ............................................................................... 147

Introduction................................................................................................................ 147
Results....................................................................................................................... 147
Absorption Spectra............................................................................................... 149
Em mission Spectra.................................................................................................. 151
Em mission Lifetim es .............................................................................................. 157
Transient Absorption Spectra .............................................................................. 161
Phototherm al M easurem ents / Triplet Yields ...................................................... 165
Decay Rate Calculations...................................................................................... 167
Electrochem istry .................................................................................................. 169
Electroabsorption Spectroscopy........................................................................... 169
D iscussion.................................................................................................................. 172
Excited-State Energetics...................................................................................... 172
How Does the Substitution Position Alter the Photophysics? ............................. 174
Sem i-Em pirical Calculations............................................................................... 177
Mulliken Theory Calculation of 4-Re-1 MLCT Dipole Moment........................ 182
Experim ental.............................................................................................................. 189
Oligom er and Com plex Synthesis........................................................................ 189
Photophysical M easurem ents............................................................................... 189
Electrochem ical M easurem ents........................................................................... 190
Sem i-Em pirical Calculations............................................................................... 190

THIOPHEN E PH OTOPH Y SICS .................................................................................... 191

Introduction................................................................................................................ 191
Results........................................................................................................................ 193
Electrochem istry .................................................................................................. 194
A bsorption Spectra............................................................................................... 197
Em mission Spectra and Decay Kinetics.................................................................. 202
Transient Absorption Spectra .............................................................................. 210
Discussion.................................................................................................................. 218
Excited-State Energetics...................................................................................... 218
Electron Transfer Energetics................................................................................ 220
Im plications of this W ork .................................................................................... 227
Experim ental.............................................................................................................. 229
M odel Com plex and Polym er Synthesis.............................................................. 229
Photophysical M easurem ents............................................................................... 229
Electrochem ical M easurem ents ........................................................................... 230

CON CLU SION S.............................................................................................................. 231

REFEREN CES ................................................................................................................ 235

BIOGRAPHICAL SKETCH ........................................................................................... 251



viii














LIST OF TABLES


Table page

2-1. Emission data for (b)ReI(CO)3(bzpy)+ ...................................................................... 53

2-2. LIOAS data for (b)Re'(CO)3(bzpy)+ ......................................................................... 58

3-1. 5-L oligomer photophysics....................................................................................... 66

3-2. 5-Re rhenium complex photophysics ....................................................................... 67

3-3. Variable temperature emission decay times of the 5-L oligomers............................ 81

3-4. Variable temperature emission decay times of the 5-Re complexes ........................ 82

3-5. 5-L oligomer LIOAS data......................................................................................... 89

3-6. 5-Re complex LIOAS data........................................................................................ 90

3-7. Triplet energies of the 5-Re complexes .................................................................... 90

3-8. 5-L oligomer and P1 triplet quenching study results................................................ 91

3-9. Triplet photophysics of P1 and 5-L oligomers ......................................................... 96

3-10. Decay rates of the 5-L oligomers.............................................................................. 96

3-11. Fluorescence intensity ratios for mixed samples ...................................................... 98

3-12. Surface coverage calculations for mixed 5-L-3 / 5-Ru-2 LB films........................ 104

4-1. 5-LP oligomer photophysics................................................................................... 127

4-2. 5-ReP rhenium complex photophysics................................................................... 128

4-3. Variable temperature emission decay times of the 5-LP oligomers....................... 136

4-4. Variable temperature emission decay times of the 5-ReP complexes.................... 137

5-1. 4-L oligomer photophysics..................................................................................... 149

5-2. 4-Re rhenium complex photophysics..................................................................... 149









5-3. Variable temperature emission decay times of the 4-L oligomers.......................... 159

5-4. Variable temperature emission decay times of the 4-Re complexes...................... 160

5-5. 4-L oligom er LIO A S data....................................................................................... 165

5-6. 4-Re com plex LIOA S data...................................................................................... 165

5-7. 4-L oligom er triplet yields...................................................................................... 166

5-8. Triplet photophysics of the 4-Re complexes.......................................................... 167

5-9. Decay rates of the 4-L oligomers............................................................................ 168

5-10.2-SA, 3-SA and 4-SA photophysical data.............................................................. 175

5-11. Semi-empirical calculations for 5-M and 4-M ....................................................... 178

5-12. Semi-empirical calculations for 5-L-1 and 4-L-1 ................................................... 180

5-13. Singlet ground state molecular orbitals for 5-M and 4-M...................................... 186

5-14. Singlet ground state molecular orbitals for 5-L-1 and 4-L-1 .................................. 187

5-15. Singlet ground state molecular orbitals for 5-L-1T and 4-L-1T ............................ 188

6-1. Thiophene model complex photophysics................................................................ 194

6-2. Thiophene polymer photophysics........................................................................... 194

6-3. Electrochemistry of thiophene complexes and polymers........................................ 197

6-4. Franck-Condon emission bandshape fitting parameters for model complexes ......203

6-5. Electron transfer rate constants for thiophene-bipyridine models and polymers....221

6-6. Electron transfer free energy changes for thiophene-bipyridine models and
polym ers.................................................................................................................. 225














LIST OF FIGURES


Figure page

1-1. BEH-PPV and 2,2'-bipyridine-containing BEH-PPV ................................................ 2

1-2. 2,2'-Bipyridine-containing PPV singlet excited-state difference absorption
spectrum in toluene..................................................................................................... 3

1-3. Aryleneethynylene-based polymer structure............................................................... 4

1-4. PPE absorption (solid line) and emission (dashed line) spectra in chloroform ..........4

1-5. Anthracene-containing aryleneethynylene polymer.................................................... 5

1-6. Absorption (solid line) and emission (dashed line) spectra in chloroform of the
polymer in Figure 1-5 with x = 0.17 ........................................................................... 6

1-7. Cyclophane-containing aryleneethynylene polymer ................................................... 6

1-8. Absorption (in dioxane) and triplet-triplet absorption difference spectra (in
benzene, 347 nm excitation) of an oligo(thiophene) series ........................................ 9

1-9. Cyclophane-containing polythiophene polymer ....................................................... 10

1-10. Poly(3-alkylthiophene) repeat structures .................................................................. 10

1-11. Poly-2,2'-bipyridine ruthenium-containing polymer................................................ 13

1-12. Aryleneethylylene-based polymers containing platinum subunits............................ 14

1-13. Ru(bpy)32+-containing PPV polymer ........................................................................ 15

1-14. Conformation change upon metal complexation...................................................... 16

1-15. Ruthenium-containing diazabutadiene polymer ....................................................... 17

1-16. PPV-type polymer with tethered ruthenium chromophores...................................... 18

1-17. Ru(bpy)32+-substituted polythiophene....................................................................... 18

1-18. Metallorotaxane-thiophene polymers ....................................................................... 19








1-19. SALOTH thiophene polymer.................................................................................... 20

1-20. Aryleneethynylene polymers containing (bpy)Re'(CO)3C....................................... 21

2-1. Basic TRTL longitudinal apparatus.......................................................................... 25

2-2. Thermal lens Gaussian probe beam divergence........................................................ 27

2-3. TRTL spectrum ofphthalazine in benzene ............................................................... 30

2-4. Time-resolved pulsed thermal lens signal obtained for 10-5 M erythosine in water.33

2-5. TRTL apparatus with probe beam absorption compensation ................................... 35

2-6. Basic photoacoustic experimental setup ................................................................... 36

2-7. Typical photoacoustic response ................................................................................ 37

2-8. Photoacoustic calibration plots ................................................................................. 39

2-9. Simulated transducer responses based on (2-11) with varying T values as
indicated, where u = 1 x 106 Hz and to= 1 ms......................................................... 40

2-10. TRTL apparatus layout ............................................................................................. 45

2-11. Ruthenium / viologen donor-acceptor system........................................................... 47

2-12. LIOA S apparatus layout............................................................................................ 49

2-13. LIOA S apparatus im ages .......................................................................................... 51

2-14. (b)Re(CO)3(bzpy)+ complexes.................................................................................. 52

2-15. LIOAS data (signal vs. time) for (b)Re(CO)s(bzpy)+ in acetonitrile ........................ 55

2-16. Corrected emission spectra of (b)Rel(CO)3(bzpy)+ in acetonitrile solution at
298 K ......................................................................................................................... 59

3-1. 5-L oligomer and 5-Re rhenium complex structures................................................ 66

3-2. Absorption spectra in THF. (a) 5-L oligomers and P1; (b) 5-Re complexes and
P4; (c) 5-ReAN-2 and 5-ReAN-3 complexes........................................................... 69

3-3. Emission spectra of the 5-L oligomers in 2-MTHF (350 nm excitation) at
temperatures varying from 298 to 80 K .................................................................... 72








3-4. Emission (dashed line) and emission polarization (solid line) r(X) spectra (350 nm
excitation) in 2-MTHF. (a) 5-L-3, 298 K; (b) 5-L-3, 170 K; (c) 5-L-4, 298 K;
(d) 5-L -4, 170 K ........................................................................................................ 74

3-5. Emission anisotropy temperature dependence observed at 525 nm. Solid circles
are 5-L-3 data, and open circles are 5-L-4 data........................................................ 75

3-6. Emission spectra of the 5-Re complexes in 2-MTHF (440 nm excitation) at
various temperatures from 298 to 80 K .................................................................... 76

3-7. Excitation (dashed line) and excitation polarization (solid line) r(X,) spectra at
80 K of 5-Re-3 2-MTHF solution at various emission wavelengths........................ 78

3-8. Normalized emission decays (intensity versus time) of 5-Re-2 at various
emission wavelengths and temperatures................................................................... 84

3-9. Transient absorption spectra of the 5-L oligomers in freeze-pump-thaw degassed
TH F solutions............................................................................................................ 87

3-10. Transient absorption spectra of the 5-Re complexes in argon bubble-degassed
THF solutions (except for 5-ReAN-2 and 5-ReAN-3, which are in CH2Cl2) ..........88

3-11. Sandros energy-transfer quenching plots (log (kq) versus acceptor energy) .............95

3-12. Emission spectra of a 1:1 mixture of 5-L-3 and 5-Re-3 (2 x 10-6 M) in 2-MTHF
at various temperatures ranging from 298 to 80 K in 20 K increments.................... 97

3-13. Photophysics of 5-Ru-2 Langmuir-Blodgett films ................................................. 101

3-14. Pressure isotherms of Langmuir-Blodgett films of 5-L-3 / 5-Ru-2 mixtures......... 103

3-15. Photophysics of 5-L-3 / 5-Ru-2 mixed Langmuir-Blodgett films.......................... 105

3-16. Effect of metal complexation to the conjugated segments of the oligomer............ 108

3-17. Proposed oligomer aggregation mechanism ........................................................... 115

3-18. Jablonski diagram of 5-Re excited state energy levels........................................... 116

3-19. Transient EPR spectra of 5-L-1 (biphenyl analogue, dotted line) and 5-ReAN-2
(solid line) at 130 K in 1:1 toluene:chloroform solution ........................................ 119

3-20. Luminescence decays of [(bpy)2Ru(bpy_pyr)]2+ in 4:1 EtOH:MeOH at various
tem peratures............................................................................................................ 12 1

4-1. 5-LP oligomer and 5-ReP rhenium complex structures......................................... 127

4-2. Absorbance spectra in THF. (a) 5-LP oligomers; (b) 5-ReP complexes............... 130








4-3. Emission spectra of the 5-LP oligomers in 2-MTHF (360 rnm excitation) at
various temperatures ranging from 298 to 80 K ..................................................... 131

4-4. Emission spectra of the 5-ReP complexes in 2-MTHF (450 nm excitation) at
various temperatures ranging from 298 to 80 K ..................................................... 134

4-5. Excitation (dashed line) and excitation polarization (solid line) r(X) spectra at
80 K of 2-MTHF 5-ReP-3 solution at various emission wavelengths.................... 135

4-6. Transient absorption spectra of the 5-LP oligomers in freeze-pump-thaw
degassed TH F solutions.......................................................................................... 141

4-7. Transient absorption spectra of the 5-ReP complexes in argon bubble-degassed
TH F solutions.......................................................................................................... 142

5-1. 4-L oligomer and 4-Re complex structures............................................................ 148

5-2. Absorption spectra in THF. (a) 4-L oligomers; (b) 4-Re complexes .................... 150

5-3. Fluorescence spectra of the 4-L oligomers in 2-MTHF (350 rnm excitation) at
temperatures varying from 298 to 80 K................................................................. 152

5-4. Emission spectra of the 4-Re rhenium complexes in 2-MTHF (400 nm
excitation) from 298 to 80 K ................................................................................... 155

5-5. Excitation (dashed line) and excitation polarization (solid line) r(X) spectra at
80 K of 4-Re-3 2-MTHF solution at various emission wavelengths...................... 158

5-6. Transient absorption spectra of the 4-L oligomers in freeze-pump-thaw
degassed TH F solutions.......................................................................................... 162

5-7. Transient absorption spectra of the 4-Re rhenium complexes in argon
bubble-degassed THF solutions (except 4-ReAN-3, which is in CH2C2) ............. 164

5-8. Electroabsorption spectroscopy of 4-Re-1 in a PMMA matrix at 80 K ................. 172

5-9. Jablonski diagram of 4-Re complexes.................................................................... 173

5-10. Stilbazole-containing complexes ............................................................................ 175

5-11. "Linear" and "bent" PPE-type polymers................................................................. 177

5-12. Arylethynylpyridine model compounds.................................................................. 178

5-13.4-Re-1 calculated LUMO molecular orbital........................................................... 184

6-1. Thiophene model complex and polymer structures................................................ 193








6-2. Cyclic voltammetry in CH3CN solution / 0.1 M TBAH, with a Pt working
electrode, Pt auxiliary electrode, and Ag/Ag (10-2 M) reference electrode.
(a) [Os(bpy)3][PF6]2; (b) P4-Os; (c) P4-Ru; (d) [Ru(bpy)3]C12 ............................. 198

6-3. Thiophene model complex and polymer absorption spectra in acetronitrile
solutions (except P4, which is in THF) .................................................................. 199

6-4. Thiophene model complex emission spectra in acetonitrile (380 nm excitation) ..203

6-5. Thiophene polymer emission (solid line) and excitation (dashed line) spectra in
optically dilute acetonitrile solution (except P4, which is in THF solution) ..........209

6-6. Transient absorption spectra of Ru(tpbpy)(bpy)22 in acetonitrile.......................... 211

6-7. Transient absorption spectra of Ru(tpbpy)32+ in acetonitrile .................................. 212

6-8. Transient absorption spectra of P4 in argon bubble-degassed THF ....................... 214

6-9. Transient absorption spectra of P4-Ru in acetonitrile............................................ 215

6-10. Transient absorption spectra of P6-Ru in acetonitrile............................................ 216

6-11. Transient absorption spectra of P4-Os in acetonitrile ............................................ 217

6-12. Thiophene-bipyridine polymer Jablonski diagram ................................................. 218

6-13. Photoinduced electron transfer process from M(P4bpy)(bpy)22+ to MV2 ............. 227














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

PHOTOPHYSICAL STUDIES OF PI-CONJUGATED OLIGOMERS AND
POLYMERS THAT INCORPORATE INORGANIC MLCT CHROMOPHORES


By

Keith A. Walters

August, 2000


Chairman: Kirk S. Schanze
Major Department: Chemistry

The use of n-conjugated polymers in various material devices has encouraged

increased research interest in their photophysical properties in recent years. The

integration of transition metal chromophores with metal-to-ligand charge transfer

(MLCT) excited states into the polymers permits easy variation of the polymer excited-

state properties, since the MLCT chromophore redox potentials are tunable via ligand

variation. With this design consideration in mind, the photophysics of two different types

of metal-organic polymers are presented.

First, a series of PPE-type aryleneethynylene oligomers containing a 2,2'-bipyridyl

unit for transition metal coordination are considered. The oligomers have a well-defined

repeat structure, unlike polymers previously studied in our group with the same subunits

that exhibited unusual photophysical behavior. These oligomers are studied by








themselves and coordinated to -Re'(CO)3CI and -Re'(CO)3(NCCH3)+OTf-

chromophores. Second, a series of poly(3-alkylthiophene) polymers containing varying

amounts of 2,2'-bipyridyl subunits are synthesized and coordinated to -Ru"(2,2'-

bipyridine)22+ and -Os"(2,2'-bipyridine)22 chromophores. The photophysical and

photothermal results of these two types of molecules are presented and interpreted,

paving the way for the design of better polymers for materials applications. Particular

attention is paid to the following:

The effect of oligomer and polymer coordination to the metal chromophore.

Upon coordination of the metal chromophore to the oligomer or polymer, the primary

absorption bands red-shift. Furthermore, organic-based fluorescence is quenched, giving

rise to an MLCT-based emission.

The effect of increasing the oligomer effective conjugation length. When the

conjugation length is increased by lengthening the oligomer, results show that anticipated

photophysical results are not obtained for the PPE-type oligomers, suggesting conjugation

breaks in the oligomer backbone via geometric twisting.

The observed excited-state equilibrium ofligand- and metal-based states (3 ;, r*

,-43MLCT). It is clear through ligand manipulation of the transition metal chromophore

that both ligand and metal-based excited states are populated upon photoexcitation, and

the observed emission and transient absorption photophysics are controlled by this

equilibrium.

The effect of oligomer and polymer structure on the observed photophysics.

Altering the repeat unit length or switching from a "linear" to "bent" 7r-backbone

structure dramatically alters the observed photophysics.


xvii














7t-CONJUGATED POLYMERS


Introduction


The unique optical and electronic properties of n-conjugated polymers have been

an area of intense research in recent decades.1 These polymers typically have high

fluorescence quantum yields,2 exhibit electrical conductivity,3 and possess non-linear

optical (NLO) properties4"6 that lead to their potential use in organic-based light emitting

diodes (LEDs),7'10 photoconductive or photorefractive devices,"'1-15 chemical sensors,16"18

and molecular electronic devices. 19'20 Two major classes of n-conjugated polymers are

considered here, polymers with a phenylenevinylene or aryleneethynylene-based subunit

and polymers with a thiophene-based subunit.

Phenylenevinylene- and Aryleneethynylene-Based Polymers

"Rigid rod" polymers with polyphenylenevinylene (PPV) or

polyphenyleneethynylene (PPE) subunits have been popular for their unique material

properties for the past 15 years. Rothberg21 performed extensive photophysical studies on

PPV-based polymers that could serve as a "molecular wire." The photoexcited electron

(i.e., exciton) can easily travel through the "electron cloud" created along the polymer

backbone by extended ni-conjugation. Typical photophysical properties for PPV as a thin

film include a broad ground state absorption centered at 400 nm and an intense 540 nm

fluorescence.21 Excited-state energies, specifically the triplet excited state, are very









difficult to measure for PPV and most other nt-conjugated polymers due to the absence of

phosphorescence. However, the energy can be determined via indirect means such as

triplet-triplet energy transfer quenching studies. A report by Monkman and coworkers22

determined the triplet energy with this method for poly(2-methoxy-5-(2'-ethyl-hexoxy)-p-

phenylenevinylene) (MEH-PPV),* calculating a value of 1.27 eV (29.3 kcal mol-'). A

previous estimate23 of triplet excited-state energies for PPV molecules placed them

between 1.2 and 1.4 eV (27.7 32.3 kcal mol'1), which agrees well with this

measurement.

A derivative of PPV, poly(2,5-bis(2'-ethylhexyloxy)-1,4-phenylene-vinylene

(BEH-PPV), has also been very popular in photophysical studies. Additionally, a PPV

polymer has been synthesized that contains a 2,2'-bipyridyl subunit for reasons discussed

later. Both polymers are shown in Figure 1-1.


OR






an' -n




Figure 1-1: BEH-PPV and 2,2'-bipyridine-containing BEH-PPV
(R = CHCH(C2H5)C6HI3 Ref 24).






See chapter 3 for a more detailed explanation of this technique when it is applied to
oligomers and polymers presented in this text.









This BEH-PPV polymer exhibited a 504 nm absorption, a sharp 560 nm emission, and a

broad singlet excited-state absorption that extends into the near-IR. The 2,2'-bipyridine-

containing polymer exhibited absorption and emission maxima at 438 and 510 nm,

respectively. The observed spectral blue-shifts are due to conjugation breaks in the n-

delocalization of the polymer backbone produced by the twisted bipyridine subunits.

This delocalization restriction is an important concept to understand in n-conjugated

polymers and will be considered in subsequent chapters. A transient absorption spectrum

of the bipyridine-containing polymer is shown in Figure 1-2. Note the broad excited-state

absorption that extends into the near-IR and the bleach that corresponds to a ground-state

n,7i* absorption.


1.6,

1.0,


0.0,
,- ........
< M / .i ,!\" -u. .e. .



400 4W SsW 600 W 700 7W
Wavelrngth (nm)

Figure 1-2: 2,2'-Bipyridine-containing PPV singlet excited-state difference absorption
spectrum in toluene (Solid line, 417 nm excitation, Ref. 24).



Another polymeric structure consisting of alternating ethynyl and aryl subunits

(polyphenyleneethynylene, PPE) was considered by Davey et al.,2 Le Moigne et al.,5'25

and Swager et al.26 having the structure shown in Figure 1-3.









OR



RO

Figure 1-3: Aryleneethynylene-based polymer structure (R = n-octadecyl, Ref. 2).



The additional rigidity in the aryleneethynylene-based polymers compared to the

phenylenevinylene samples allowed for higher emission quantum yields by decreasing the

nonradiative decay rate constant (knr), which could make them more useful in conjugated

polymer applications. Absorption spectra for the polymer shown in Figure 1-3 exhibited

a sharp 452 nm absorption that is assigned as a n,n* transition of the conjugated

backbone. A corresponding sharp emission band with a 482 nm maximum is observed,

as shown in Figure 1-4.


Wavelength, nm


Figure 1-4: PPE absorption (solid line) and emission (dashed line) spectra in chloroform
(Ref. 26).








Keeping the "molecular wire" idea in mind, Swager and coworkers26 synthesized

aryleneethynylene-based polymers containing varying amounts of anthracene repeat units

as shown in Figure 1-5.





OC16ft ^




Figure 1-5: Anthracene-containing aryleneethynylene polymer (Ref. 26).


Photophysical studies of these polymers showed that excitation into absorption bands

associated with the polymer backbone produced emission typically observed for

anthracene and a dramatic reduction in the polymer-based fluorescence. For example, a

polymer with a structure corresponding to x = 0.17 in Figure 1-3 has the absorption and

emission spectra shown in Figure 1-6.

This mixed polymer exhibited the same absorption and emission observed for the

PPE polymer (Figure 1-3), but the presence of new absorption and emission bands at 527

and 549 nm, respectively, result from the anthracene moiety. This observation suggests

that the exciton was efficiently "trapped" by the anthracene subunits. This trapping could

lead to emission or energy transfer to other substituents, which would be utilized in LED

or NLO applications. Therefore, polymers could be synthesized containing unique

subunits (like anthracene in this example) to manipulate (i.e., tune) the excited-state

properties of the polymer. Furthermore, model systems where anthracene moieties were








only present at the ends of a PPE 20-mer still exhibited pronounced anthracene emission,

indicating very efficient energy transfer along the polymer backbone (e.g., "exciton

hopping").26


300 400 500 600 700 800
Wavelength, nm


Figure 1-6: Absorption (solid line) and emission (dashed line) spectra in chloroform of
the polymer in Figure 1-5 with x = 0.17 (Ref. 26).


Zhou and Swager16 continued the defect-trapping idea with aryleneethynylene

polymers containing a cyclophane-based "receptor" as seen in Figure 1-7.




R 0 ., o000




Figure 1-7: Cyclophane-containing aryleneethynylene polymer
(R = CON(C8H17)2, Ref. 16).








The cyclophane polymer exhibited a 427 nm absorbance and intense ((jem = 0.70) 459 nm

emission. The presence of organic molecules that can associate within the cyclophane

(e.g., methyl viologen) effectively quenched the polymer emission. As little as 60 jLM

methyl viologen quenched the polymer fluorescence by an order of magnitude, and 0.1

mM completely quenched the emission. This quenching is due to the formation of

effective "exciton traps" analogous to the anthracene moieties discussed earlier, resulting

in efficient quenching of entire polymer strands with a relatively small amount of the

associating molecule.

Polythiophene-Based Polymers

Another series of n-conjugated polymers that have received much attention for

their optical properties are polythiophenes. Yamamoto and coworkers first reported the

conductivity of polythiophene in 1980,27 and its ease of oxidation made this polymer very

popular for molecular wire and doping applications. Photophysical data for

polythiophene in solution is difficult to measure, as thiophene oligomers containing six or

more thiophene rings have extremely poor solubilities. For this reason, small molecular

weight oligothiophenes and substituted polythiophenes have been studied that circumvent

this solubility issue.

An exhaustive study by Becker and coworkers2-'30 illustrated the effect increased

backbone nt-conjugation has on the observed photophysics. The photophysics of

oligothiophenes ranging in size from one to seven thiophene rings were presented, and

many trends are apparent. The absorption and fluorescence spectra both exhibited red-

shifts with increasing oligomer size (from 232 to 441 nm for absorption; from 362 to 522

nm for emission in dioxane). Emission quantum yields and lifetimes also increased in the








larger oligomers, suggesting an increase in the nt-delocalization of the oligomer backbone.

Both absorption and emission maxima were found to be inversely related to the oligomer

size, allowing for the estimation ofpolythiophene values (490 nm absorption; 580 nm

emission). The transient absorption spectra of the oligothiophenes also red-shifted with

increasing oligomer size, with the largest oligomer resembling the PPV spectrum in

Figure 1-2. Absorption and transient absorption spectra of the oligothiophene series are

shown in Figure 1-8.

The absence of phosphorescence in the oligothiophenes eliminated the possibility

of direct determination of their triplet excited-state energies. However, a photoacoustic

calorimetry technique was used to indirectly determine the triplet energy, which

decreased from 2.23 eV to 1.60 eV (51.5 36.9 kcal mol"1) as the oligomer size was

increased from two to seven thiophene rings.30 The energy was found to be inversely

related to the oligomer size, allowing the polythiophene value to be extrapolated (1.43

eV, 33.0 kcal mol1). This energy is very similar to the PPV values listed above.

Swager's use of cyclophane subunits in aryleneethynylene-based polymers (Figure

1-7) was also used with a polythiophene backbone as shown in Figure 1-9. The

cyclophane-containing polythiophene exhibited a 520 nm absorption and 624 nm

emission that is considerably weaker than the PPE polymer (em = 0.066). This emission

intensity decrease is due to the greater flexibility of the polythiophene backbone, which

provides an alternative non-radiative mechanism for excited-state deactivation through

molecular motion. The polymer fluorescence was also quenched by organic molecules


t See chapter 2 for a more detailed explanation of this technique and chapters 3 and 5 for
its application to determine triplet excited-state energies and yields.










(e.g., methyl viologen) as before, indicating efficient exciton trapping by the cyclophane

subunits. The quenching rate is smaller for this polymer than the PPE polymer, however,

due to the weaker polythiophene emission intensity.


300 400 500
X/nm


-4


800


400 500 600

X (nm)


700 800


Figure 1-8: Absorption (in dioxane) and triplet-triplet absorption difference spectra (in
benzene, 347 nm excitation) of an oligo(thiophene) series. The a number indicates the
number ofthiophene rings in the oligomer. (Ref. 28-29)


a-3


A


q


* I
















Figure 1-9: Cyclophane-containing polythiophene polymer (R = Cj0H21, Ref. 16).


While polythiophenes have many interesting properties, their solubilities are very

poor. Furthermore, they can be oxidized by atmospheric oxygen, limiting their

processibility and stability in materials applications.31 Elsenbaumer and coworkers32

synthesized an alkylated derivative of polythiophene in 1986 that was soluble and

considerably more stable. Four different coupling structures are possible in these

alkylated polymers, which are illustrated in Figure 1-10.


R R
S
S S
R n
Head-to-Tail-Head-to-Tail
Coupling (HT-HT)
R R


s s I s
R
Head-to-Tail-Head-to-Head
Coupling (HT-HH)


R R
S
S S
bs I ( Is,
R n
Tail-to-Tail-Head-to-Tail
Coupling (TT-HT)
R R
S
S S
R n
Tail-to-Tail-Head-to-Head
Coupling (TT-HH)


Figure 1-10: Poly(3-alkylthiophene) repeat structures (Ref. 33).


0,0'- 0^' O,.0 0-- 0








It was found that the increased structural homogeneity improved the conductivity

and optical properties of the polymer by increasing the effective conjugation lengths

within the polymer strands.33'34 Random connection patterns prevented the polymer from

achieving the coplanarity necessary for extended 7t-conjugation via steric interactions. In

recent years, synthetic techniques have been refined to produce highly regiospecific

polythiophenes for materials-based applications.33'35 Absorption spectra of HT-HT

poly(3-alkylthiophenes) in chloroform solution exhibit a broad absorption band centered

at 436 nm. Varying the alkyl chain lengths from hexyl to dodecyl did not change the

solution absorption spectra but induced a red-shift of the solid-state absorption spectrum

by 15 nm from the shortest to longest alkyl chain.33 Note that the absorption maximum

of a TT-HH poly(3-decylthiophene) is 312 nm in chloroform,36 significantly blue-shifted

from the HT-HT polymer and confirming the need for regiospecific polythiophenes to

achieve the maximum extended conjugation. The polymer extended it-conjugation

exerted a similar effect on 3-alkylthiophenes as seen earlier on the oligothiophenes, as the

major absorption band of a series of oligo(3-octylthiophene)s in chloroform red-shifts

from 302 to 405 nm with increased oligomer size from two to six thiophene rings. This

trend indicates a consistent lowering of the LUMO energy.37

Unlike the PPV and PPE-type polymers, phosphorescence has been observed at

low temperature (18 K) for poly(3-hexylthiophene) by Xu and Holdcroft.38'39 A sharp

826 nm phosphorescence was observed, leading to a calculated triplet excited-state

energy of 1.50 eV (34.6 kcal mol'1). This value is higher than the MEH-PPV and

polythiophene triplet energies (1.26 eV), which is surprising since the alkylated thiophene

is a more planar polymer, which should increase the delocalization and lower the energy.








This observation could be due to the regiospecificity of the phosphorescence sample, but

Xu and Holdcroft reported that various regiochemistries were investigated with similar

spectral results. Also, the MEH-PPV triplet energy was determined by qualitative

quenching studies,$ which could result in a large error.

MLCT-Incorporated n-Conjugated Polymers


The initial photophysical work on 7t-conjugated polymers, coupled with the desire

to more easily control their excited-state characteristics, led to the idea of introducing

inorganic MLCT (metal-to-ligand charge transfer) chromophores into the polymer

backbone. These chromophores have excited states that can easily be tuned by ligand

substitution, potentially allowing a greater capacity to tune the polymer excited

state(s).40-42 Following the initial idea, the synthesis and photophysical properties of

these metal-organic nt-conjugated polymers have rapidly grown in interest.43"41

Phenylenevinylene- and Aryleneethynylene-Based Polymers

Yamamoto and coworkers first suggested the introduction of MLCT

chromophores into n-conjugated polymers during his studies on poly-2,2'-bipyridine.49"52

The bipyridine repeat unit allows easy ligation of ruthenium, nickel, copper, and iron

chromophores, as shown with the -Ru"(bpy)22 chromophore (bpy = 2,2'-bipyridine) in

Figure 1-11.






SIn the study, when a triplet acceptor (tetracene, ET = 1.27 eV) did not quench the triplet-
based transient absorption of MEH-PPV, the polymer triplet energy was "estimated" to be
that value.22





















Figure 1-11: Poly-2,2'-bipyridine ruthenium-containing polymer (Ref. 50).


The resulting metal-containing polymers exhibited electrochemical data largely

representative of the MLCT chromophores, including Ru" -> Ru" oxidation and

2,2'-bipyridine reduction. Since these polymers were synthesized for their photocatalytic

and photoelectrochemical properties, little photophysical work other than an absorption

spectrum in methanol was published. This absorption spectrum contained bands

originating from both the polymer n,n* and ruthenium MLCT transitions at 373 and 450

nm, respectively. A copper(II)-containing polymer was also synthesized where a single

copper atom had the capability to ligate two adjacent polymer strands. Absorption

spectra of the copper-containing polymer exhibited a 20 nm red-shift in both the polymer-

based tn-7r* absorptions and the metal-based MLCT transition when compared to model

monomeric systems, indicating lowered LUMO energy levels due to increased

delocalization.

An alternative method for introducing transition metal chromophores into

7t-conjugated polymers involves direct metal center substitution into the polymer chain.








Wittmann and coworkers53'54 synthesized aryleneethynylene-based polymers containing

Pd[P(C4H9)3]2 or Pt[P(C4H9)3]2 subunits as shown in Figure 1-12.


P(C4HO3

T-o-=c- --==--o ).

P(C4,.)3


Figure 1-12: Aryleneethylylene-based polymers containing platinum subunits
(M = Pd or Pt, Ref. 53).


This synthetic approach produces very consistent polymer products and interesting

photophysical results. An intense 380 nm singlet and weaker 510 nm triplet ground state

absorption were observed in solution studies of this polymer, which is red-shifted from

the model monomer spectrum (345 nm). This red-shift reflects a clear increase in

delocalization across adjacent n orbitals in the polymer backbone. A broad 520 nm

luminescence was also observed from the polymer sample. However, due to their

position within the polymer backbone these metal chromophores lack the tunabilityy"

options available in other MLCT-based chromophores that are attached to the polymer

backbone like the ruthenium chromophore in Figure 1-11.

Work pioneered by Yu and coworkers produced a significant advance in MLCT-

containing n-conjugated polymers by introducing the well-known and characterized

Ru(bpy)32+ and Os(bpy)32+ chromophores into a PPV-type polymer shown above (Figure

1-1) through an ingenious Heck coupling reaction.43'44'55 The polymer structure is shown

in Figure 1-13.


















Figure 1-13: Ru(bpy)32+-containing PPV polymer (R = n-heptyl, Ref. 43).


These polymers exhibit interesting photoconductivity, photorefractivity, and NLO

properties. The all-organic polymer (x = 0, y = 1 in Figure 1-13) exhibited an intense

7r,7* transition absorption at 470 nm, while the all-metal polymer (x = 1, y = 0) had a 550

nm "MLCT" absorption. A mixed polymer (x = 0.1, y = 0.9) absorption spectrum

exhibited a superposition of the two bands. Extensive work was performed on the

material properties of these polymers listed above, but the studies did not extensively

probe the basic photophysical properties of the polymer excited statess.

Further work was performed on these polymers by Wasielewski and

coworkers,24'56 including work where the polymer backbone was used as an ion sensor.18

The completed metal ion induced a conformational change in the 2,2'-bipyridine polymer

subunit, which is twisted and serves as a break in the polymer n-conjugation as discussed

earlier. The bipyridine was coplanar after complexation, resulting in a conjugation

increase within the polymer as seen in Figure 1-14. This conjugation increase led to

differing photophysical properties that signal the presence of the analyte ion (e.g., red-


The molar absorptivity for this transition (ca. 90 x 103 M'I cm') is rather high for an
MLCT transition. However, the high concentration of ruthenium and the extended
delocalization of the polymer backbone might contribute to its high value.








shifted absorption and emission bands) due to a lowering of the LUMO. For example,

when nickel(H), zinc(l), or palladium(II) ions were titrated into a solution containing the

2,2'-bipyridine-containing PPV, the polymer 7t,7t* 450 nm absorbance red-shifted

between 50- 100 nm depending on the metal ion. The ionochromic effect exhibited in

these polymers proved to be an excellent ion-sensing device.56






OOR

OR Mfl+11+ M =
-,E1




Mn+ R
// / I \\N

Figure 1-14: Conformation change upon metal complexation (R = decyl, Ref. 18).


In the wake of the PPV research, other 7t-conjugated polymers containing

inorganic MLCT chromophores have also been investigated. Rasmussen et al.57 made

ruthenium-containing polymers with a poly-diazabutadiene / 2,2'-bipyridine backbone as

seen in Figure 1-15. An absorption spectrum of the polymer showed an intriguing blue-

shift from a dimer model oligomer (from 480 to 465 nm in DMF). However, the polymer

band was significantly broader, suggesting a myriad of accessible electronic transitions.

The observed emission spectrum remained the same (sharp 666 nm band) for the two

systems, but the polymer quantum yield was one-fourth the dimer value. This trend







suggested that increased nonradiative decay or decreased intersystem crossing to the

emissive 3MLCT might result from the extended 7t-conjugation.


/ Rupy)2

N --

N\ /FNdc;

Ru(bpY)2 X

Figure 1-15: Ruthenium-containing diazabutadiene polymer (Ref. 57).


More recently, Wong and Chan58 synthesized PPV-type polymers that have
ruthenium chromophores attached via an alkoxy chain, as shown in Figure 1-16. This

polymer configuration provides even greater ligand substitutional flexibility but removes

the MLCT chromophore from direct interaction with the polymer n-conjugation, thus
limiting its effects on the polymer excited statess. The purpose of these polymers was to

form metal-organic LEDs, with the chromophore not serving as a "tuning control" for the
polymer excited states) but as a dopant to produce the electrogenerated luminescence. A
(x = 0.1, y = 0.9) polymer exhibited a 444 nm absorption and 606 nm emission in DMF
solution, which is very similar to monomeric Ru(bpy)32+ photophysics. These data
indicate little electronic interaction between the polymer and MLCT chromophore.

LEDs fabricated from these polymers exhibited good current-voltage properties
and serve as an excellent starting point for tunablee" LEDs by varying the ruthenium








ligands. Clearly, the topic of MLCT-incorporated 7t-conjugated polymers is of great

recent interest, and many other polymer structures are available for exploration.


Figure 1-16: PPV-type polymer with tethered ruthenium chromophores
(Ru = Ru(bpy)32+, Ref. 58).


Polythiophene-Based Polymers

Introducing MLCT chromophores into thiophene-based polymers has also been

studied, but to a lesser degree than the PPV and PPE-based polymers. Zhu and

Swager59'60 synthesized a Ru(bpy)22+-containing polythiophene via ligation to a 2,2'-

bipyridine polymer subunit, as seen in Figure 1-17.




/ I (PF6)2n


Figure 1-17: Ru(bpy)32+-substituted polythiophene (Ref. 59).


The monomer repeat unit of the unmetallated polymer exhibited a sharp 400 nm

absorption in methylene chloride, which is blue-shifted from the estimated native








polythiophene value (490 nm) for the same reasons discussed above for the

2,2'-bipyridine-containing PPE polymers. Further work by Zhu and Swager17'61 focused

upon thiophene polymers containing metallorotaxane centers with zinc or copper ions, as

shown in Figure 1-18.









/0 0




Figure 1-18: Metallorotaxane-thiophene polymers (M = Zn2 and Cu2, Ref. 17).



These rotaxanes exhibited marked improvement in stability over the bipyridine-

containing polythiophenes (Figure 1-17) and improved conductivity over native

polythiophene. Detailed photophysics, however, were not presented in this study.

Reddinger and Reynolds synthesized another novel thiophene-based polymer

containing MLCT chromophores.62'63 In these polymers, a nickel or copper chromophore

was completed to a SALOTH ligand that was incorporated into the thiophene backbone

as shown in Figure 1-19. This polymer showed excellent conductivity properties, but

again its photophysics were not the major focus of the reported research.









HC-30 M.0CH3
N N

Ssy

Figure 1-19: SALOTH thiophene polymer (M = Ni" and Cu", Ref. 62).



Previous Group Work

Based on the previous work described above, it was obvious to our group that

while many different inorganic MLCT chromophore-containing ni-conjugated polymers

were being synthesized and applied in various materials applications, little detailed

photophysical work had been performed to explore their excited state energies and

dynamics. To that end, a project was initiated to synthesize polymers combining some of

the ideas explored by previous groups. The work by Yamamoto and coworkers49-52 and

Yu and coworkers43"44'55 incorporating MLCT chromophores through a 2,2'-bipyridine

subunit in the polymer backbone was desirable since it afforded maximum tunability

when selecting MLCT chromophores such as ruthenium, rhenium, and osmium

complexes. Also, the increased rigidity of the aryleneethynylene-type polymers was more

favorable than PPV-type structures. This rigidity would provide larger transition dipoles

and hopefully more pronounced photophysical behavior. Therefore, a polymer structure

combining both of these elements was devised and implemented.

A series of r-conjugated aryleneethynylene polymers with varying incorporated

amounts of the well-characterized -(bpy)Re'(CO)3Cl chromophore41 were synthesized via








Sonogashira coupling64 and their photophysical properties investigated in our lab.45'46'65

The polymer structures, along with typical polymer weights obtained from GPC

experiments, are shown in Figure 1-20.


OR


RO n
P1 : Mw = 37 kg mole1, Mn = 14 kg mole1, PDI= 2.7

OR OR


RO xn \ / RO yn- n
Re (CO)3CI
P2 : x = 0.10, y = 0.90; M = 21 kg mole1, Mn = 8.8 kg mole1, PDI= 2.3
P3: x = 0.25, y = 0.75; Mw = 16 kg mole"1, Mn = 7.9 kg mole1, PDI = 2.1
P4: x =0.33, y =0.67; M = 26 kg mole"1, Mn = 11.3 kg mole"1, PDI = 2.3
P5 : x = 0.50, y = 0.50; Mw = 16 kg mole"1, Mn = 7.8 kg mole1, PDI = 2.0

R = n-C18H37

Figure 1-20: Aryleneethynylene polymers containing (bpy)ReI(CO)3Cl (Ref. 46).



Metal-organic polymers P2 P5 exhibited many unique photophysical properties,

including a red-shifted absorption band and unique long-wavelength luminescence when

compared to the "all organic" polymer P1. These observations were believed to arise

from a dnr (Re) -+ n* (bpy-polymer) MLCT transition as seen in the PPV-based polymers

presented above (Figure 1-13), which is typically observed for transition metal MLCT

chromophores.41 Studies on model monomeric compounds that duplicated the repeat

structure of the polymers initially supported this theory. However, certain photophysical








results were puzzling. For instance, the introduction of the rhenium MLCT chromophore

into the polymer backbone decreased the polymer fluorescence quantum yield and

lifetime, which would be expected due to the chromophore acting as an "exciton trap" as

described above. However, polymer-based fluorescence was not completely quenched in

even the P5 polymer, which was unexpected. Polymers P2, P3, and P5 were synthesized

by a random copolymerization process, resulting in an inability to accurately characterize

the polymer segment sequencing. Specifically, it was unclear whether the transition

metal segments were homogeneously distributed throughout the polymer or segregated

into "all organic" and "all metal" sections within the synthesized polymer. The

inefficient fluorescence quenching suggested that a heterogeneous polymer was being

produced by this procedure, allowing the organic polymer segments to behave as if the

metal chromophore was not present. Further synthetic developments allowed for the

synthesis of polymer P4, which has a known (organic, organic, metal) repeat structure.

Nonetheless, it was evident that further work based on model systems containing this

repeat structure was necessary to better interpret the polymer photophysical observations.

Scope of This Work


To further understand the photophysics observed for P1 P5, a series of

well-defined oligomers containing various lengths of the original polymer repeat structure

were synthesized using a novel iterative synthetic scheme based around palladium-

mediated coupling reactions. The detailed photophysical results of both free oligomers

and oligomers bound to the Re(CO)3C1 chromophore are presented herein. Next, the

repeat units and geometries of the oligomers were varied to see how these changes affect








the observed photophysics. Particular attention is paid to the oligomer conjugation length

influence and/or the possible formation of aggregates on the observed photophysical

properties. Many spectroscopic techniques, including absorption, emission, transient

absorption, electroabsorption spectroscopy, and transient EPR were utilized to probe the

molecular excited statess. Also, in a collaborative project with Dr. Stephan Guillerez

and Lise Trouillet at CEA-Grenoble, the photophysical properties ofpoly(3-

alkylthiophenes) with the capacity to complex MLCT chromophores through an

integrated 2,2'-bipyridine subunit were studied in order to investigate the influence of the

transition metal on their excited-state properties. The polymers are similar in structure to

the Swager polymer shown in Figure 1-17 but with the added alkylation stability. Before

these photophysics are discussed, however, a class of techniques that utilize the evolution

of heat after photoexcitation to determine excited-state energetic is presented. This

technique, photothermal chemistry, has received little attention in the study of inorganic

complexes but is successfully utilized in the photophysical study of our PPE-type

oligomers and polymers.














PHOTOTHERMAL CHEMISTRY


Photothermal chemistry involves the study of electronic transitions through the

radiation of heat instead of light. The majority of photothermal chemistry studies in the

literature rely on one of two techniques: Thermal lensing spectroscopy and photoacoustic

spectroscopy. Thermal lensing spectroscopy involves a change in the sample refractive

index due to released heat, resulting in the diffraction of a probe laser beam.66'67

Photoacoustic spectroscopy uses a piezoelectric transducer to analyze pressure waves in a

sample caused by the emission of heat.68'69 The main advantage of studying excited states

with photothermal studies is the lack of dependency upon the emission of light, which

greatly increases the number of molecules that are amiable for study.

Both techniques have distinct advantages and disadvantages. Photoacoustic

spectroscopy has a shorter (nanosecond to microsecond) observation time window than

thermal lensing spectroscopy and requires external calibration, resulting in additional

sample runs and increased experimental time.70 Time-resolved thermal lensing (TRTL)

spectroscopy, however, has a long (tens of microseconds) observation time window and

requires no external calibration.71 Furthermore, photoacoustic spectroscopy does not

need to correct for probe beam absorption and can more readily study complex, multiple-

process excited-state behavior. Both techniques will be addressed in turn, followed by

their application to the study of inorganic and organic photophysics.









Theory


Time-Resolved Thermal Lensing

The premise of TRTL is very simple. A sample is irradiated with a pump laser,

producing an excited electronic state. A second probe laser is then directed through the

photoexcited sample. These two beams are commonly in a longitudinal (colinear)

geometry, but they can also be applied in a transverse (perpendicular) configuration. Any

heat evolved by the sample excited state decay(s) will cause a change in the sample

refractive index and subsequent probe beam refraction (i.e., the formation of a "thermal

lens"). A decrease in the probe beam center intensity can therefore be related to heat

released by the sample.67 The pump beam is removed from the optical path by a filter or

dispersing prism, and the probe beam center is usually isolated by a pinhole or knife edge

for intensity measurement. Figure 2-1 shows a basic TRTL apparatus.



w e 1 .,.
Pijo I- z ^--------------------
nttilplst^[


Figure 2-1: Basic TRTL longitudinal apparatus (Ref 70).








The thermal lens theory

The thermal lens effect (also known as "thermal blooming") was first reported by

Gordon and coworkers over 30 years ago.72 It was initially considered a hindrance to

other laser spectroscopic methods, but Gordon determined that the degree of laser beam

refraction was related to the sample solution refractive index. Since the refractive index

of a liquid changes with temperature, the induced refraction can be related to heat given

off by the photoexcited sample. The thermal lens does not form immediately upon the

release of heat and slowly decays based on the thermal conductivity of the sample, so

time-resolved experiments can also be performed.66

The thermal lens focal length in a "steady state" equilibrium, f(oo), is given in

(2-1). This value can be used in (2-2) to calculate the thermal lens focal length at time t,

f(t), during a TRTL experiment.

f/ (00 7kco2 (2-1)
f(oo)= ----- n7k \
2.303PAan/(
( \ /pJ ( (2-2)

f(t)=f(oo + 8kT (2-2)


In (2-1) and (2-2), k is the sample thermal conductivity (W cm'" K'1), co is the Gaussian

probe laser beam spot size (cm2), P is the probe beam power (W), A is the sample

absorbance, /i is the refraction index variation with temperature, p is the sample

density (g cm"3) and Cp is the specific heat of the sample (J g-' K1). These equations do

not take into account any sample luminescence, and all excitation energy is assumed to be








released as heat. Appropriate corrections can be used if any appreciable luminescence

occurs concurrent with the emission of heat.66

If a TEM00 Gaussian laser beam is used for the probe, equations can describe the

beam diffraction based upon the thermal lens effect. The variables used in ensuing

equations are visually defined in Figure 2-2. The relative probe beam area change at the

pinhole, A(02, is defined in (2-3),73 while the beam center intensity change at the pinhole,

Albc, is defined by (2-4).66



Pinhole


Propagation, Z


Figure 2-2: Thermal lens Gaussian probe beam divergence (Ref. 66).


2(Z1)Zc
Z +(Zl)


(2-3)








AIb 2"303P( q// ]A
Al _-2 3 = 2.303EA (2-4)

In (2-3) and (2-4), X is the probe laser wavelength and Zc is the confocal distance

Q ~/ ). E is a simplified instrumental value of the various constants in (2-3), since

they should not change during the experiment. Therefore, a variation of sample
absorbance should produce a linear relation and allow the sample refraction change with
temperature to be determined. Both (2-3) and (2-4) are considered the fundamental
TRTL theory equations, but they are rarely used in everyday experimental practice.
Another treatment of TRTL theory74 discusses the relationship of the sample
refractive index change and the commonly-used TRTL signal, S(t), which is defined in
(2-5). The proposed equation for this relationship, assuming longitudinal geometry of the
pump and probe beams, is given in (2-6).

S(t)= V -V(t) (2-5)
Vo0

) 8aElIz Uri/ 4(x-Vt)2 -2(x-vxt)2 (26)
SL(t) 0 8c2E/ 22- 2 D Jexl a2 D (2-t)
71PCp [a2 +8Dt]2 ,- a2+8Dt ) a + 8-t

In (2-5), V0 is the intensity of the probe beam center before pump beam excitation and
V(t) is its intensity at time t after pump excitation. Therefore, S(t) can vary between 0 (no
beam divergence) and 1 ("complete" theoretical beam divergence). In (2-6), the sample is
assumed to be analyzed perpendicular to the sample flow which has a velocity of vx, a is
the absorption coefficient, Eo0 is the pump beam energy, li is the pump/probe beam
interaction length within the sample, a is the probe beam Gaussian radius, and D is the








sample thermal diffusivity (min2 s'l). An equation similar to (2-6) can also be derived for

the transverse (perpendicular) orientation of the pump and probe beams. Both (2-4)66 and

(2-6)74 show the relationship between the sample refractive index change (e.g., evolution

of heat) and the degree of probe beam diffraction. Although these equations are complex,

it is not necessary to use such quantitative measurements of thermal lensing to

calorimetrically determine excited state energies and excited state process quantum

yields.

A simplified calculation method

The calculation scheme presented here for TRTL studies was first used by

Braslavsky and coworkers in a study of singlet oxygen quantum yields of various organic

sensitizers.75 If the analyte under study involves a single, long-lived triplet state

following intersystem crossing from an emissive singlet state (many organic

photochemical systems of interest fall into this category), then (2-7) can be applied to

determine the intersystem crossing quantum yield (ODisc).

Uslow O IscET
w- (2-7)
UTota Ee nDfEs

In (2-7), ET is the triplet excited state energy, Eex is the pump laser energy, Onf is the

fluorescence quantum yield, and Es is the singlet excited state energy. If either Disc or ET

is known from other photophysical measurements, TRTL can be used to determine the

unknown parameter. Uslow and UTotai values are obtained directly from the TRTL

spectrum. A sample TRTL response of phthalazine, which qualifies for the use of (2-7),

measured in benzene by Terazima and Azumi71 illustrates Uslow and UToai and is shown in








Figure 2-3. TRTL intensity (S(t) from (2-5)) is plotted versus time after pump beam

excitation.




USUM//-




19
IU-


Z UTOT





0 10 20
Time I Ls


Figure 2-3: TRTL spectrum ofphthalazine in benzene (Ref. 71).



In Figure 2-3, UToti represents the entire heat given off by the sample after pump

laser excitation (occurring at t = 0 4ts), while Usow represents the heat gradually given off

by the nonradiative decay of the triplet excited state to the singlet ground state. The fast

heat (UTotaj Us0ow) immediately given off at time zero represents fast processes (e.g.,

fluorescence and intersystem crossing) with lifetimes faster than the acoustic transit time

(Ta) of the sample75 (Ta = -; R = radius of probe beam, Da = velocity of sound in the
Da

sample medium), which was around 50 ns for Terazima and Azumi.71 A third








component, a gradual decay of the TRTL signal on the order of milliseconds resulting

from thermal conductivity within the sample, is not shown in Figure 2-3.*

The true beauty of this method is that no calorimetric standards are required to

measure (Disc (or ET), so long as the other variables in (2-7) are determined by other

spectroscopic techniques. A plot of log[UTotw S(t)] versus time can yield a linear plot

from which the triplet lifetime can be calculated. The only specific requirement for this

calculation method is that the triplet excited state lifetime must be longer than about 4Ta.

(200 ns in the Terazima and Azumi example)71 but shorter than the thermal conductivity

decay time of the sample (usually a few milliseconds). If the excited state lifetime is

outside these boundaries, Usow cannot be distinguished from UFast in the TRTL spectrum.

It is important to note that (2-7) presumes that fluorescence is the only alternative

decay process to the release of heat.68 If phosphorescence (e.g., emission from the triplet

excited state) is observed instead of fluorescence, (2-7) must be adapted to allow for this

new excited-state deactivation pathway, as shown in (2-8).

Uslow ET(I-Oem) 28
UTOt Eex -ET +ET+ _Oem) (2-8)

In (2-8), (3,em is the triplet phosphorescence quantum yield. The intersystem quantum

yield is assumed to be unity, which is valid for most inorganic chromophores due to spin-

orbit coupling induced by the presence of heavy atoms.76 Equations like (2-8) can easily

be derived for other photochemical systems with multiple excited state processes.

However, for complex systems photoacoustic spectroscopy is likely to be more

informative.


* See Figure 2-4 for a TRTL spectrum with this component.








Limitations and instrumental considerations

One problem experienced in TRTL spectroscopy results from the presence of

singlet oxygen. If singlet oxygen is produced by the excited state quenching process, its

decay is readily observed in the thermal lens response (and possibly falsely interpreted as

an excited-state decay of the analyte).77 While this may be a hindrance in many

experiments, TRTL can provide an easy singlet oxygen detection method if it is an

expected product in a photochemical process. However, if this decay is not desired

rigorous degassing of all samples should be performed prior to experimentation to

eliminate the possibility of its production.

The main culprit by far in TRTL that leads to errant signals is the absorption of

the probe beam by the sample. The excited state of most inorganic chromophores

produced by photoexcitation readily absorbs at visible wavelengths typically used for the

probe laser, which results in an erroneously high TL signal.6 Chartier and coworkers

have also observed abnormal TRTL signals with erythrosine that are attributed to an

"78
excited-state triplet-triplet absorption at the probe beam wavelength.78 This errant signal

was characterized by a rapidly decaying component in the TL signal that was readily

eliminated with the addition of oxygen to quench the excited state absorption. These

abnormal TL signals are obvious in the spectra in Figure 2-4. The excited state

absorption error can be reduced with an appropriate apparatus design, as described below.

The majority of all TRTL experimentation is performed with an apparatus similar

to that in Figure 2-1. An extensive study by Berthoud and coworkers analyzed the

optimal beam geometries for the pump and probe laser beams.79 They determined that for

maximum TRTL sensitivity and resolution the pump beam should be focused in the








sample cell, while the probe beam should be focused about 10 cm in front of the cell.

Since the thermal lens spreads the probe beam, if its focus is before the sample the beam

will already be diverging through the sample cell. Therefore, the beam divergence will

further increase after passing through the sample thermal lens, increasing the sensitivity

of the technique. If the probe beam is focused after the cell, the thermal lensing signal

will be inverted relative to the typical TRTL spectrum (i.e., the probe beam center

intensity increases as heat is given off). If the probe beam focus is after the sample the

beam will be diverging after the thermal lens before it reaches the beam waist, resulting

in a smaller probe beam after the beam focus.74 With these optimal conditions, it was

determined that the detection limit for TRTL could be as much as two to three orders of

magnitude lower than those determined for absorption spectrophotometry ( 1 x 10-8 M

for a strongly absorbing species).79'80


30 -













0 40 So 0 TM 10 20 30 40

--n P ---- ms.......


Figure 2-4: Time-resolved pulsed thermal lens signal obtained for 10-5 M erythosine in
water (Ref. 78). (a) air saturated; (b) oxygen-saturated; (c) nitrogen-saturated.








Several other instrumental concerns must be considered. The pinhole radius must

be at most 1/10 the radius of the probe beam to ensure accurate measurement of only the

beam center intensity. This pinhole is placed about 2.5 3 m from the sample to allow

maximum probe beam divergence and, consequently, instrumental sensitivity. Also,

experimentation81 concluded that the probe beam radius should be approximately four

times the size of the pump beam radius for optimal response. The laser beam diameter

manipulation cannot simply be done with apertures, as Fresnel diffraction rings would be

created which would severely distort the intensity measurement. Instead, a laser

telescope should be used to properly size the pump and probe beams.81 The sample is

commonly in a flow cell to ensure a constant supply of ground state analyte molecules

and reduce sample degradation from extended periods of photoexcitation.67 The majority

of the referenced studies use the longitudinal pump and probe beam geometry with both

beams overlapping each other in a collinear and concentric manner within the sample

cell.

Cambron and Harris devised a more complicated TRTL apparatus to help alleviate

the concern of any possible probe beam absorption.73 Their apparatus is illustrated in

Figure 2-5. The key feature of their design is the use of a second PMT detector (after L5

in Figure 2-5) that measures the intensity of the entire probe beam after it passes through

the sample. This "time-resolved" reference signal corrects for any laser fluctuations and,

more importantly, sample excited-state absorbance of the probe beam after pump

excitation. This design feature will be implemented in our study.
















IH Fif V M
LJH Lf


~~4y~L7
U2 L4 A S P

Figure 2-5: TRTL apparatus with probe beam absorption compensation (Ref. 73).


Photoacoustic/Laser-Induced Optoacoustic Spectroscopy

Instead of monitoring heat evolution through a refractive index change,

photoacoustic spectroscopy "listens" for the shock waves that travel through the sample

medium as heat is released. The pressure waves are detected with a piezoelectric

transducer that is placed in contact with the sample cuvette, as seen in Figure 2-6.

Heavily damped transducers are used to keep the relaxation time short and allow for

better temporal resolution while minimizing the influence of shock wave reflections

within the sample cell on the observed signal.82 The transducer response versus time

illustrating the shock waves produced by heat emission is shown in Figure 2-7. The

initial signal spike in the figure indicated by the arrow is the only usable data in this plot,

as all subsequent responses are reflections of the shock waves off the sides and bottom of

the sample cuvette.

Initially, it was believed that photoacoustic techniques would not be as practical as

TRTL for our research purposes, as it has a limited time window and required the









purchase of piezoelectric transducers and a preamplifier. However, photoacoustic

spectroscopy has the marked advantage over TRTL measurements in that no

implementations are needed to correct for any sample excited-state absorption of the

sample under investigation. Photoacoustic spectroscopy measures pressure waves instead

of light, so transient light absorption is not a concern.


LWS


Figure 2-6: Basic photoacoustic experimental setup (Ref. 69).









0.20
0.1$5
0.10o


-0.00
-0.05
-0.10
-0.1S
0


25 50 7S 100 125 150 175 200
Time (s)


Figure 2-7: Typical photoacoustic response (Ref 69).



Early photoacoustic techniques


Early photoacoustic experiments sought to determine the conversion efficiency of

photoexcitation energy to heat (a) as determined in (2-9).

hue =(
In (2-9), all relaxation processes of a particular excited-state system are included in the

summation, where Di is the excited state process quantum yield and Ei is the retained

energy of that process. A conversion efficiency of 1 indicates all the excitation energy is

released as heat only during the experiment timescale.t A specific quantum yield or

process energy can be determined from (2-9) (if all other parameters are known by other

methods) by calculating a in (2-10).


U =al Kc (ll-O-A) (2-10)



t Common examples of these a = 1 systems are benzophenone, ferrocene and crystal
violet.83








In (2-10), U is the initial photoacoustic signal spike intensity (e.g., the "heat" given off by

the sample), IL is the laser power, and K is an experimental constant that is determined

from a calorimetric standard with a known a value.

If U for an unknown system is plotted versus 1 10- a line is obtained with a
IL

slope equal to Ka. If an additional plot is constructed with data obtained from a

calorimetric standard and compared to the plot of the unknown system, a for the

unknown can be calculated as illustrated in Figure 2-8. The conversion efficiency can

then be applied in (2-9) to determine the unknown quantum yield or excited state energy

for the analyte molecule.

While this calculation technique is straightforward, it fails to provide any time-

resolved information for multiple excited-state processes, and the use of calibration

standards can greatly complicate the procedure and increase the chances for error.

Therefore, our attentions were turned to a modified photoacoustic technique, Laser-

Induced Optoacoustic Spectroscopy (LIOAS).

Laser-induced optoacoustic spectroscopy

LIOAS observes in a time-resolved manner the pressure waves produced by either

heat released from a photoexcited sample or structural volume changes following

excitation. The evolution of heat is central to our interest in the technique, and

corrections for volume changes will be discussed later. The evolution of the transducer

response to pressure waves with time (V(t)) is defined in (2-11).84









^ yo
S//
| 1.0 00 /


/ +
S0.5-



p I
0 0.2 0.4 0.6
1 1'A

Figure 2-8: Photoacoustic calibration plots. Circles are benzophenone (reference) data
points, while crosses are pyridazine (unknown) data points (Ref. 83).
f_1







h0A (.+J e/-t J -tf sinUt,
VWt) 4=0 22 exp( To Ut0''4
+ (2-11)

In (2-11), h-A is an instrumental constant, u is the transducer characteristic oscillation

frequency, To is the transducer relaxation time, T is the excited-state process lifetime, and

S= Equation (2-11) was used to model simulated transducer responses with
various excited-state lifetimes, and the responses are shown in Figure 2-9.
various excited-state lifetimes, and the responses are shown in Figure 2-9.












00









~10 -- 2. 5 u- --

0 SO 100 IS0 0n0
CHANNEL


Figure 2-9: Simulated transducer responses based on (2-11) with varying T values as
indicated, where u = 1 x 106 Hz and TO = 1 ms (Ref. 84).



It can clearly be seen that any transducer response falls into one of three

categories. Exceedingly short timescale processes (t < 1 ns, the fast lifetime response

region) all produced the same waveform. Medium lifetime processes (T = several ns to a

few u.s) resulted in a response phase shift and amplitude decrease, and long lifetime

processes (x = several ups and greater) became indistinguishable with the baseline. Also,

the delineation between lifetime categories is governed by both the characteristic

frequency of the transducer and the previously defined acoustic transit time of the sample

(Ta),85 which represents the theoretical lower limit of detectable excited-state lifetimes.

In order to extract information from the transducer response signal, deconvolution

using an iterative nonlinear least squares algorithm82 is necessary. This technique

requires three separate data sets for one measurement: 1) A baseline signal; 2) A fast

lifetime reference signal (i.e., a sample which releases all excitation energy as heat in a








single fast lifetime process); and 3) A sample signal. To minimize the use of correction

factors in the data analysis, the sample and reference signals are in the same solvent and

with matched excitation absorbances. These signals are normalized by subtracting the

baseline signal and dividing by both an absorbance factor (1 10-A) and the average

excitation laser pulse energy. Only the first few oscillations are selected for analysis

since subsequent oscillations are acoustic reflections from the sample cell walls. In the

deconvolution process, fast lifetime excited-state processes will be grouped together into

one component with a meaningless lifetime fit but the correct amplitude (i.e., the total

heat fraction released by the sample from all fast lifetime processes). Medium lifetime

processes produce meaningful amplitudes and lifetimes. Long lifetime processes should

not be detected by the transducer. While LIOAS is used mostly in aqueous media

biological applications, the technique can be applied to organic and inorganic systems in

nonaqueous solutions to distinguish between multiple excited-state processes.

Accounting for solution volume changes

As noted earlier, the main possibility for LIOAS measurement error involves

transducer response correction for any sample structural volume changes (AVR). These

volume changes can be due to either photoexcited molecule structural changes or solvent

molecules ordering around the excited analyte. If we assume that each of the components

obtained from the deconvolution process discussed previously contains contributions

from both thermal and volumetric changes, (2-12) can be derived.86


Eex(Pi = iEi + I0iAVR,iCP) (2-12)








In (2-12), (pi is the deconvolution amplitude for excited state process i, Cp is the

solvent heat capacity, p is the solvent density, and a is the solvent thermal expansion

coefficient. The first term in (2-12) is the contribution due to emitted heat, while the

second term is due to structural volume changes. These terms can be separated on the

basis of altering the solvent thermal expansivity parameters. The majority of LIOAS

studies focusing on reaction volume changes85'86 were done in aqueous solution, which

allows for easy manipulation of these parameters due to the significant temperature

dependence of a in water. The same parameter manipulation can be achieved in

nonaqueous environments by making several LIOAS measurements in a series of similar

solvents. This strategy was used in studies with a series of n-alkane solvents.87'88 Of

course, the assumption must be made that the analyte photochemistry is similar in each of

the solvents in the series, so care must be taken when selecting the series. If a plot is

c p
made of Eempi versus pp, a linear relation is expected with a slope of (IiAVR,i (the
a

volumetric component of the signal) and an intercept of iEi (the thermal component of

the signal).

It is important to note that Hung and Grabowski88 suggested the assumption that

all observed LIOAS signals are thermal in nature leads to only "small calculation errors"

when the system under investigation undergoes no net photochemistry and exhibits only

minimal structural change upon photoexcitation. While this assumption might appear to

cover the majority of our systems of interest, the possibility that AVR might contribute to

the observed LIOAS signal must be recognized and anticipated.


a is also referred to as 13, the cubic expansion coefficient.








Instrument Design and Calibration Studies


Time-Resolved Thermal Lensing

An apparatus was set up to study TRTL with various organic and inorganic

systems of interest in our group. Before experimentation was undertaken, initial

calibration studies were first performed on the TRTL apparatus involving the triplet

excited-state energy measurement of various organic molecules and studying two

previously investigated donor-acceptor systems that are described below.

Apparatus setup

A diagram of the final apparatus is shown in Figure 2-10. The third harmonic of a

Nd:YAG laser (355 nm, Spectra-Physics GCR-14) is used as the pump beam, which is

attenuated with neutral density filters to an energy of approximately 100 -200 PJ pulse-.

This pump beam is directed through a plano-convex focusing lens that is mounted on a

two-axis positioning stage to simplify beam alignment. The focus of the pump beam is

generally in the center of the sample cell, although its position is tweaked using the

positioning stage to give the cleanest TRTL signal. A 1 mJ frequency-stabilized CW

He-Ne laser (633 nm, Aerotech 100-SF) is used as the probe beam, which is expanded

through two lenses to double the beam radius. The ratio of probe to pump beam radius in

our apparatus is 10:1. The expanded probe beam is directed through a piano-convex

focusing lens so that the focus of the beam is 10 cm in front of the cell based on the

Berthoud study.79 The probe and pump beams are combined in a colinear and concentric

fashion with the use of a 50% reflecting 633 nm beam splitter. The beams travel through

a 1 cm pathlength quartz sample cell and are then separated by the use of a dispersing








prism. The probe beam continues through a shutter to a pellicle beam splitter, which

reflects 8% of the beam through a piano-convex focus lens, an OG-590 cutoff filter,

diffuser (to minimize any possible position dependency of the PMT detector), and a 633

nm interference filter before being detected with a R446 PMT. This PMT serves as the

experiment reference signal, which should correct for any transient absorption seen in the

excited sample. The remaining bulk of the probe beam travels 2.5 m until it reaches a

1.19 mm diameter pinhole. The center of the probe beam travels through an OG-590

cutoff filter and a 633 nm interference filter before being detected with a 1P28 PMT.

This PMT serves as the experiment sample signal.

The two PMT signals are simultaneously recorded on a Tektronix TDS 540 digital

oscilloscope using a 10 Hz sampling rate, with typically 1000 laser shots averaged during

each data collection cycle. The PMT signals are internally terminated (50 0) with a 20

MHz internal bandwidth filter to reduce signal noise. The two decay traces are fed into

an analysis program written by the author in Microsoft Visual Basic 6.0, where the two

individual signals are initially normalized on a scale of 0 to 1. The normalized reference

signal is then subtracted from the normalized sample signal as specified in (2-5) to give

the observed TRTL signal, which is renormalized for final presentation to the user.












Key:
1. Right Angle Prism
2. ND Filter
3. Piano-Convex Pump
16 Focus Lens (f = 75.5)
19 4. UV Coated Mirror
5. Piano-Convex Probe
Expander Lens 1 (f = 5.0)
18 6. Piano-Convex Probe
Expander Lens 2 (f= 10.1)
7. Piano-Convex Probe Focus
Lens (f = 35.0)
8. 632.8 nm Beam Splitter
9. Beam Dump
10. Sample Cell
11. Dispersing Prism
SI12. Shutter
15 14 13. 8% Reflecting Pellicle
13 /Beam Splitter
13 14. Reference PMT Diffluser/
12 Plano-Convex Focus Lens
(f = 10.0)
15. Reference PMT
1 16. Standard Mirror
/0Note: The distance from 10 17. Standard Mirror
10 to 19i approx. 2.5 m. 18. Pinhole
19. Signal PMT


Id
17

8 7 6 5
h I He Ne Laser I
9 10.0 14.4 Table 1


















Figure 2-10: TRTL apparatus layout (all dimensions in cm).




Calibration studies


Initial TRTL work involved the triplet energy measurement of several common


organic triplet sensitizers in both polar and non-polar nitrogen-degassed solutions using








(2-7). Benzophenone, phenanthrene, anthracene, and 9-methylanthracene were selected

as the triplet sensitizers. Unfortunately, triplet energies obtained with our instrument

failed to agree well with literature values for all the sensitizers except benzophenone.

Errors as high as 50% were obtained in some cases. The ineffective TRTL measurement

of these energies could stem from the rapid (several ns) excited-state decay of these

sensitizers, which is well below the sample acoustic transit time (200 ns). Furthermore, a

recurring problem with our apparatus involved obtaining a pure reference signal from the

reference PMT, where it was very common to see some evidence of thermal lensing. The

typical cure for bad reference signals was a careful adjustment of the probe and pump

beam geometries in the sample cell so that a good signal was recorded by the sample

PMT while as clean a reference signal as possible was recorded by the reference PMT. It

was not uncommon to obtain only one "good" experimental run during an hour of

constant measuring, as the beam positioning slowly drifted over time. While this trial-

and-error method was time consuming and tedious, it was the only effective way to

achieve reasonable data.

A second calibration study involved the use of donor-acceptor systems that had

considerably longer-lived excited states. Both tris(2,2'-bipyridine)Ru" / methyl viologen

(MV2)40'89 and (2,2'-bipyridine)Re'(CO)3(4-benzylpyridine)+ / diaza[2.2.2]octane

(DABCO)90'91 were studied with a significantly higher degree of success than the organic

triplet sensitizers. The excited state processes of the ruthenium / viologen system is

illustrated in Figure 2-11.







1IbI2+
IRu b(bp )(bpy)2 2.

3Ru"'(bpy-)(bpY)22,q
/ +MV2+ .
S3[Ru.'(bpy)(bpy)23+ + MV i]-- p- Free Ions
+hu (om
/em




Ru"(bpy)22

Figure 2-11: Ruthenium / viologen donor-acceptor system.



The U Sl"o calculation for this system can be greatly simplified by making the paraquat
UToa

concentration high enough to effectively quench all ruthenium emission (i.e., in Figure

2-11, (Iem = 0 and (Dq = 1). It is also assumed that the intersystem crossing yield ((isc) is

unity.76 The Us"-" calculation is now straightforward, as shown in (2-13).
U Total

U SIw= ( sepEFI (2-13)
U Total Ehu

If previously determined values for cDsep (0.31) and EFI (free ion energy; 1.69 eV = 2.7 x

10-19 J molecule') are used, the expected UsOW- ratio is 0.15.40,89
U Total

Our ruthenium / paraquat measurements obtained a USlo ratio of 0.20, which had
U Total
a lower error than the organic triplet sensitizer measurements. Furthermore, our rhenium

/ DABCO measurements, which would exhibit the same behavior described in Figure








2-11,90,91 almost exactly matched the predicted results (0.41 predicted; 0.42

experimentally determined). Eventually, TRTL was abandoned for LIOAS when the

excessively tedious process to correct for sample transient absorption proved to not be

worth the uncertain results obtained with our apparatus. However, our TRTL apparatus

was successfully used for the triplet energy determination of polymer P1, which is

described in chapter 3.

Laser-Induced Optoacoustic Spectroscopy

Apparatus setup

The layout for our LIOAS apparatus is illustrated in Figure 2-12. The

instrumental demands for LIOAS are straightforward compared to TRTL. A pellicle

beamsplitter diverts 8% of the 355 nm Nd:YAG radiation (Spectra Physics GCR-14)

through a stack of neutral density filters (typically 10% and 25% ND filters are used). A

very low excitation energy (8 40 pJ pulse') is required in LIOAS studies to prevent

multiphoton events. The remaining portion of the pump beam is sampled with an energy

meter (Scientech S310 with a P09 Probe) to allow for energy normalization. After

passing through a 2 mm slit to minimize beam wandering effects, the pump beam is

focused with a plano-convex lens (f= 10.0 cm), producing a beam diameter of 0.25 mm

within the sample cell. The transducer is held to the side of the sample cuvette

perpendicular to the pump beam propagation by means of an in-house designed cell

holder. A film of vacuum grease is applied between the transducer and cell wall to better

facilitate the relay of acoustic waves. The cell holder is mounted on a linear translation

stage to allow variation of the excitation region distance from the transducer surface

within the sample. Varying this distance allows for temporal movement of the transducer







response from any initial laser RF noise. Since the cell / transducer geometry cannot

change between reference and sample experiments, the cell is firmly clamped in place and

a solvent delivery system is constructed to distribute rinsing solvent, nitrogen purging

gas, and sample solutions without moving the cell. The sample cell was typically rinsed

with flowing solvent for 5 minutes and dried with flowing nitrogen gas between

experiments.


8% Reflecting
Energy Pellicle BeamSplitter Dms
Meter --- ^ ~----------I rs
10& 25 /oTP
ND Filters Slit


Piano-Convex >
[-- --i Lens (f = 10 cm) ,
Computer \ /\


FOscilloscope ...Preamplifier]14 Beam a:i
-- NY J Dump Z


Figure 2-12: LIOAS apparatus layout.


Two transducers are used with differing characteristic frequencies, 1 MHz

(Panametrics V 103) and 5 MHz (Panametrics V 109). The higher frequency transducer

should be more sensitive to shorter-lifetime excited-state processes. The signals are

intensified with a Panametrics 5670 40 dB preamplifier and recorded with a Tektronix

TDS 540 digitizing oscilloscope. Initial data processing, instrument control and data

normalization are conducted with software written in Microsoft Visual Basic 6.0 by the

author. Sound Analysis 3000 software is used to deconvolute the processed acoustic








waves and provide amplitudes and lifetimes.92 Pictures of the LIOAS apparatus are

shown in Figure 2-13.

Calibration study (b)Re'(CO)3(bzpy)+ triplet energies

A detailed LIOAS calibration study was conducted to determine the triplet

metal-to-ligand charge transfer (3MLCT) energy of a series of rhenium complexes,fac-

(b)Re'(CO)3(bzpy)+, where b is a substituted diimine ligand and bzpy is 4-benzylpyridine

(Figure 2-14). This inorganic chromophore has been widely studied, and its

photophysical properties are well known.93 Furthermore, the 3MLCT energy is easily

varied over several kcal mol'1 by changing the substituted diimine.41'42 Since the

(b)Re'(CO)3(bzpy)+ 3MLCT state is emissive, its spectrum can serve as a second

independent means of measuring its energy through Franck-Condon emission lineshape

fitting.76'91 The series of complexes also has different 3MLCT lifetimes due to their

varying excited state energies, so the delineation between fast, intermediate, and slow

lifetime processes detected by our LIOAS apparatus can be studied and confirmed.

The 3MLCT Energy. The 3MLCT energy for the (b)Re(CO)3(bzpy)+ complexes,

along with other emissive transition metal complexes, is traditionally determined with a

single-mode Franck-Condon line-shape analysis of the observed 3MLCT emission band

observed at ambient temperature.76'91 Therefore, experimental emission spectra for the

complexes obtained from nitrogen-degassed acetonitrile solutions were fitted to (2-14).


IM )= { h-- haSm I _)V exp 41n2 v-Voo +V (m m. (2-14)
vo 00 m AVo, I / 2
















































4 TI ple Daiwery,-Manif4i
A., a-"Wftw





Inlet Control Valve 0 i:,;A C control Valve
1, Flush Solvent 1. Wast, Beaker
2 Wrogen Gas 2 Syringe
Sample S)rinqe


Figure 2-13: LIOAS apparatus images.









'2 1 CO (b) = (tmb): R1,=CH3, R2 = CH3
N !| ,\CO (b) = (dmb): R, = H, R2= CH3
SRe' (b) = (bpy): R1 = H, R2 = H 0
N1 c0 (b) = (damb): RI = H, R2 =)& NEt2
K- 0
R^ N
2 (b) = (deb): R, = H, R2= OEt







Figure 2-14: (b)Re(CO)3(bzpy)+ complexes.


In (2-14), I(V) is the relative emission intensity at energy v, V00 is the zero-zero

transition energy (i.e., the 3MLCT energy), Vm is the average medium frequency

vibrational mode quantum number, h(om is the medium frequency acceptor modes

average coupled to the MLCT transition (1450 cm'1),76 Sm is the Huang-Rhys factor (i.e.,

the electron-vibration coupling constant), and AV0,1/2 is the individual vibronic band

half-width. The Voo values obtained from (2-14) for the (b)ReI(CO)3(bzpy)+ series are

listed in Table 2-1, and fitted emission spectra are shown in Figure 2-16 along with the fit

parameters. These fit parameters are consistent with a previous study conducted in our

group on similar complexes.91










Table 2-1: Emission data for (b)Re'(CO)3(bzpy)+.
(b)" en Tern / s Vnax / Cm-1 b VoO / cm-1 c
(kcal mol'1)
tmb 0.25 1473 18700 19400
(55.5)
dmb 0.06 274 17450 18375
(52.5)
bpy 0.045 208 17210 17975
(51.4)
damb 0.026 116 16700 17280
(49.4)
deb 0.0145 93 15360 16050
(45.9)
'Argon-degassed CH3CN solutions, 298 K. Estimated errors: Team, 15%; TVm, 5%; v, + 100cm';
V0, 500 cm"-. bEmission maximum. C0-0 emission energy estimated by Franck-Condon analysis (2-14).



Since the 3MLCT excited state lifetime for the (b)Re'(CO)3(bzpy)+ complexes

falls within the medium lifetime category of LIOAS responses, the energy of the lowest

MLCT excited state can be independently calculated from both of the two expected

components recovered from the LIOAS data deconvolution analysis. In principle, the

first "fast" heat deposition process (ti and 1) corresponds to heat released when the

singlet MLCT state ('MLCT, the excited state produced by photon absorption) relaxes to

3MLCT with unit efficiency. The second heat deposition process (xr2 and 02) corresponds

to heat released concomitant with nonradiative decay of3MLCT. Based on these

definitions, the amplitudes can be related to the 3MLCT energy by (2-15) and (2-16).

S=Eh -ET (2-15)
Ehv


0= ET(1-(em) (2-16)
Ehv








In (2-15) and (2-16), Ehv is the excitation energy (355 nm = 80.5 kcal mol'), ,em

is the emission quantum yield from 3MLCT and ET is the 3MLCT energy. LIOAS decays

were obtained from degassed acetonitrile solutions with both the 1 MHz and 5 MHz

ultrasonic transducers of each complex in the (b)Re(CO)3(bzpy)+ series. Figure 2-15

illustrates typical analysis results for the (b)ReI(CO)3(bzpy) series. Table 2-2 contains

the average normalized amplitudes ()) recovered from deconvolution analysis of four

independent LIOAS measurements on each complex, the lifetime of the medium lifetime

heat-deposition component (t2), and ET values calculated from the experimental Oi values

with (2-15) and (2-16). Figure 2-16 shows the emission spectra and compares 3MLCT

energies for the five (b)Re(CO)3(bzpy)+ complexes obtained from the LIOAS data using

both transducers (four ET values for each complex) and the emission Franck-Condon

analysis.

The Validity of LIOAS Measurements Several assumptions must be made in order

to assess the potential use of LIOAS data for the determination of excited state energies.

First, the emission spectra and Franck-Condon bandshape analysis is assumed to provide

the best available estimate for the 3MLCT energy, which is less than ideal due to the

convoluted mathematical fit. However, since this methodology is widely accepted in the

literature it is deemed sufficient for a yardstick in evaluating the LIOAS technique for this

purpose. Second, our LIOAS data analysis neglects contributions to the acoustic wave

arising from the potential volume change that occurs concomitant with 3MLCT decay as

discussed earlier.












ST2 1077ns 0.5= 645 ns

(AL
QE 0.25-
O 0.25-
0 & 0
-J' -f^ ^j 0-^
-0.25-
-0,25
5 b0 100 150 25i 20. 0 5b 100 150 20I 20
Channel Channel

1 c. (dmb), 1 MHz 1 d. (dmb), 5 MHz
0.75. /A = 0.3364 .75 0 i= 0.3326

2 = 0.6892 )2= 0.6191
|o. Jr2 = 279ns 0. T2 = 273 ns
E 0255
0.250.

-0..2-
0--0
-025 -0.2- v
-0.
5- .5
a nn150 1 .. 25 0 o 10 150''- 2W 0
Channel Channel

A e. (bpy), 1 MHz f. (bpy), 5 MHz
0.7- A 0 = 0.3318 0.75 ) = 0.3556
ID 02= 0.6368 2 4 = 0.6662
ST2 / 2=197ns o0.& 2= 185ns
.o. -o. j

0)

0-0-0
-0.5- 0.25

0 I50 100 150 200 250 0 50 100 150 200 250
Channel Channel
Figure 2-15: LIOAS data (signal vs. time) for (b)Re(CO)3(bzpy)+ in acetonitrile. Solid
(highest intensity) lines are the ferrocene reference waveform, dotted lines are the sample
waveform, and dashed lines are the deconvolution fit. Note that TI = 10 and 1 ns for the 1
and 5 MHz transducers, respectively.













S5t// 2= 106ns 0.5 TC2 = 105 ns



o 0 0


.y5 -025/ J t
-0. ___ V ____V
6 50 100 WI* 150 200 250 0 50 150 6" 200 .. 250
Channel Channel
1t
i. (deb), 1 MHz 1 j. (deb), 5 MHz
o.75 Ol = 0.2760 075 6 = 0.5701
0 05 \2 = 0.6222 ()2 = 0.5131
"o 0.5-2
T2= 41 ns 0.5 T2 =79 ns

E) 0.25o.2
D.1
E 0.2&

o 0-
J 0 25-I

-0.5-25

0 50 100 150 200 250 0 50 100 150 200 250
Channel Channel
Figure 2-15 Continued



Three major conclusions can be drawn concerning the measurement of excited

state energies and lifetimes using the LIOAS apparatus and deconvolution analysis.

1. LIOAS Measurements are accurate only when the excited state lifetime is

greater than 200 ns. It can clearly be seen in Figure 2-16 that for the complexes with

tmb, dmb, and bpy ligands, the 3MLCT energies derived from LIOAS and emission

spectral fitting are in reasonable agreement. In stark contrast, the LIOAS energy values

for complexes with damb and deb ligands vary widely and are in poor agreement with the

emission spectral fitting energies. The 3MLCT lifetimes of the three complexes with








concurrent energy measurements range from 210 to 1500 ns, while the two disparate

complex lifetimes range from 90 to 120 ns (see Tem in Table 2-1 and the x2 deconvolution

component in Table 2-2). This result clearly indicates that the validity of the LIOAS data

is strongly influenced by the probed excited state lifetime, and the lower lifetime limit for

reliability with our apparatus is T > 200 ns. This limit is directly related to the acoustic

transit time (Ta) of the LIOAS apparatus as defined above. If a beam radius of 0.25 mm

and a velocity of sound in acetonitrile of 1300 m s-1 is assumed for our instrument, an

acoustic transit time of 192 ns is obtained. This acoustic transit time is not small enough

to accurately resolve the fast relaxation of the 'MLCT state and the nonradiative decay of

the 3MLCT state for complexes with 3MLCT lifetimes less than 200 ns (i.e., the damb

and deb complexes).

2. Excited state energies derived from deconvolution of the second medium

lifetime deconvolution component are less precise and accurate compared to those

derived from the first fast lifetime deconvolution component. The error bars shown in

Figure 2-16 clearly indicate that the precision and accuracy of the energies determined

from (2 and (2-15) are generally poorer compared with those derived from 01 and (2-16).

Simulated LIOAS responses derived by reconvolution of two decay components similar

to those observed for (b)Rel(CO)3(bzpy)+ indicate that 01, is primarily influenced by the fit

quality in the initial spike of the LIOAS signal, while 02 is determined mainly by the fit

quality in the subsequent LIOAS signal oscillations after the initial peak. This secondary

oscillation region of the LIOAS signal is complex and relatively noisy in our recorded

LIOAS data, which inherently decreases the precision of the fitted (2 values.









Table 2-2: LIOAS data for (b)Rel(CO)3(bzpy)+.

1 MHz Transducer
Liganda r2 T2/ ns ET / cm-1 b ET / cm-l
(kcal mol-1) (kcal mol')
tmb 0.2698 0.02 0.4402 0.05 1109 294 20570 630 16540 1850
(58.8 1.8) (47.3 5.3)
dmb 0.3281 0.02 0.6267 0.09 264 11 18610 450 18780 2550
(53.2 1.3) (53.7 7.3)
bpy 0.3059 0.04 0.6410 0.01 196 9 19550 1110 18890 420
(55.9 2.9) (54.0 1.2)
damb 0.35340.08 0.5908 0.06 103 6 182202310 170701750
(52.1 6.6) (48.8 5.0)
deb 0.3070 0.02 0.6493 0.07 56 9.7 19520 700 18540 2100
(55.8 2.0) (53.0 6.0)

5 MHz Transducer
Liganda 02 T 2/ns ET / cm-1" b ET / cm-1 C
(kcal morl"1) (kcal morl')
tmb 0.3122 0.03 0.5123 0.04 772 180 19380 730 19240 1400
(55.4 2.1) (55.0 4.0)
dmb 0.3486 0.04 0.6302 0.03 249 17 18360 1010 18890 870
(52.5 2.9) (54.0 2.5)
bpy 0.3587 0.04 0.6780 0.05 197 14 18050 1150 20010 1430
(51.6 3.3) (57.2 4.1)
damb 0.4238 0.03 0.5475 0.04 1116 16230 910 15840 1120
(46.4 2.6) (45.3 3.2)
deb 0.5156 0.12 0.5499 0.10 79 9.5 13640 3360 15700 2800
(39.0 9.6) (44.9 8.0)
'Argon-degassed CH3CN solution, 298 K. Reported values are averages of four runs of fresh sample and
ferrocene reference solutions, and errors are a. T1 fixed at 10 ns for the 1 MHz transducer and 1 ns for the
5 MHz transducer. bTriplet energy calculated from the first deconvolution amplitude (2-15). cTriplet
energy calculated from the second deconvolution amplitude (2-16).









1.00 a. (tmb)

075~~ g"o' o"11 y
S.7 s=1.1 9400 \cm
0.50 Au = 2900 cm
0.25 '0

0.00

0.75


0.00 i. i ii i
1.00 b.(dmb)
00 U00 = 18375 cm1


S 0.75 1.1
D 0.50 Au,1=2900 cm






0.50
G 0.25



0
"S o.oo '^ ^ ,..-



E" 1.00 d. (damb)
U u' ;oo= 17975 cml


0.75 1.1
L 0.0051 Aui l 2800 cm 1
c 02 02

0
z 0.00



1.00 e. (deamb)
1U ^





0.75 S=0.9
0 -5 S =1.1



0.50 Au2 = 2550 cm-1

S0.25---I
0.50 0 i 7







12 14 16 18 20 22 24
1.1 cm1 u Emission ucm-1
0.7 LIAS = 1 MHz
A LI AS2550 MHz




O LIOAS 1,5 MHz
0.256 r-\ A^^-
0.00 ^ ^ ^ ~
12 14 16 18 20 22 24

Emission Energy 103 cm- 0 EmsionS .TM
LIOAS i01 1 MHz
0 WIAS 0 5 MHz
LIOAS 02, 5 MHz

Figure 2-16: Corrected emission spectra of (b)Re'(CO)3(bzpy)+ in acetonitrile solution at
298 K. Points are experimental data, and solid lines are spectra calculated using Franck-
Condon analysis (2-14) with the fitting parameters listed on each spectrum. 3MLCT
energies are presented on each plot with acr errors. (a) b = (tmb); (b) b = (dmb);
(c) b = (bpy); (d) b = (damb); (e) b = (deb).








3. Lifetimes can be accurately measured with LIOASfor medium lifetime

decay processes. It is clearly seen in Tables 2-1 and 2-2 that the 3MLCT lifetime

independently obtained by LIOAS and emission measurements is in reasonable agreement

for the complexes with dmb and bpy ligands. These complexes represent the medium

lifetime processes that are correctly measured by the transducer. For a slow lifetime

process (i.e., the tmb complex) the transducer detected a signal that is partially damped by

the transducer, resulting in an erroneously low lifetime. This damping increases for the 5

MHz transducer due to its higher characteristic oscillation, which leads to the larger

observed errors. The narrow range of lifetimes correctly measured by LIOAS suggests

that traditional (e.g., optically-based) methods are more suitable for determining these

values.

This calibration study demonstrates the validity of LIOAS measurements to

measure excited state energies and lifetimes so long as the excited-state lifetime is higher

than the acoustic transit time of the apparatus (ca. 200 ns). LIOAS will be further used to

determine the triplet energies and/or yields of several nt-conjugated oligomers and

inorganic complexes discussed in chapters 3 and 5.

Experimental


(b)ReI(CO)3(bzpy)+ Synthesis

Synthesis of (b)Rel(CO)3Cl. This synthesis proceeded via analogous procedures

for each complex, so a representative procedure is given. For (4,4',5,5'-tetramethyl-2,2'-

bipyridine)Re'(CO)3Cl, 300 mg of Re(CO)5CI (0.833 mmol, prepared by literature

method),94 194 mg 4,4',5,5'-tetramethyl-2,2'-bipyridine (tmb, 0.916 mmol, 1.1








equivalents), and 15 mL toluene were placed in a roundbottom flask. The solution was

stirred and refluxed under nitrogen for 1.5 hours, during which time the off-white

solution turned a golden yellow. A yellow precipitate formed, and the mixture was stirred

at room temperature under nitrogen overnight to complete the reaction. The precipitate

was filtered with a medium porosity glass frit, washed with three toluene washes, and

dried under vacuum for several hours to remove excess toluene. 400 mg of

(tmb)Re'(CO)3CI was collected (93% yield). The remaining complexes were synthesized

with similar yields.

Synthesis of (b)Rel(CO)3(bzpy)+. The synthesis of each complex is similar for

the entire series, so extensive details are only given for the (tmb)Rel(CO)3(bzpy)+

complex. All other complexes were synthesized with analogous procedures but varying

reaction times.

[(4,4',5,5'-tetramethyl-2,2'-bipyridine)Re'(CO)3(bzpy)J[OTf]. In a

roundbottom flask 200 mg of (tmb)Rel(CO)3CI (0.386 mmol) and 124 mg silver triflate

(0.425 mmol, 1.25 equivalents) were dissolved in 15 mL methylene chloride. The

solution was stirred in the dark at room temperature overnight to complete the

counteranion exchange. A dark yellow solution resulted with a fine white silver chloride

precipitate. The precipitate was removed by filtration through celite on a medium

porosity glass frit. The filtrate was placed in a clean roundbottom flask, and 185 mg of 4-

benzylpyridine (1.16 mmol, 3 equivalents) was added while the solution stirred. The

solution was stirred at room temperature for 24 hours, during which time its luminescence

dramatically increased when excited with UV light. A dull yellow precipitate was

obtained after rotary evaporation of the solvent, which was washed twice with ether and








dried under vacuum. A light yellow powdery precipitate, [(tmb)ReI(CO)3(bzpy)][OTfj,

resulted (52 mg, 17% yield). 'H NMR (CDC13) 8 2.40 (s, 6H, methyl), 2.56 (s, 6H,

methyl), 3.91 (s, 2H, benzylic), 7.10 (d, pyridyl), 7.20 7.40 (m, phenyl), 7.93 (s, tmb),

7.98 (d, pyridyl), 8.57 (s, tmb).

[(4,4'-dimethyl-2,2'-bipyridine)Re'(CO)3(bzpy) [OTf]. A yellow powdery

precipitate, [(dmb)Re'(CO)3(bzpy)][OTf], resulted (89% yield). 'H NMR (CDCl3) 8 1.60

(s, 6H, methyl), 3.90 (s, 2H, benzylic), 7.10 (d, 2H, pyridyl), 7.20 7.40 (m, phenyl), 7.52

(d, 2H, dmb), 7.92 (d, 2H, pyridyl), 8.70 (s, 2H, dmb), 8.82 (d, 2H, dmb).

[(2,2'-bipyridine)Re'(CO)3(bzpy)J [OTfJ. A bright yellow crystalline precipitate,

[(bpy)Re'(CO)3(bzpy)][OTf], resulted (62% yield). 'H NMR (CDCl3) 6 3.90 (s, 2H,

benzylic), 7.09 (d, pyridyl), 7.20 7.40 (m, phenyl), 7.78 (dd, 2H, bpy), 8.00 (d, 2H,

pyridyl), 8.35 (d, 2H, bpy), 8.95 (dd, 2H, bpy), 9.03 (d, 2H bpy).

[(4,4'-bis(diethylamino)-2,2'-bipyridine)Re'(CO)3(bzpy)] [OTfl. A dark yellow

crystalline precipitate, [(damb)Re'(CO)3(bzpy)][OTf], resulted (50% yield). 'H NMR

(CDCI3) 8 1.21 (t, methyl), 3.47 (qq, methylene), 3.92 (s, 2H, benzylic), 7.08 (d, pyridyl),

7.10 7.40 (m, phenyl), 7.59 (d, damb), 8.12 (d, pyridyl), 8.42 (s, damb), 9.01 (d, damb).

[(4,4',5,5'-diethoxy-2,2'-bipyridine)Re'(CO)3(bzpy)][OTfl. A dark red

crystalline precipitate, [(deb)Re(CO)3(bzpy)][OTf], resulted (low yield, but it was the

most difficult by far to synthesize). 'H NMR (CDC13) 1.48 (t, 6H11, methyl), 3.88 (s, 2H,

benzylic), 4.55 (q, 4H, methylene), 7.09 (d, pyridyl), 7.20 7.40 (m, phenyl), 8.09 (d, 2H,

pyridyl), 8.27 (d, 2H, deb), 8.98 (s, 2H, deb), 9.24 (d, 2H, deb).


F- -








(b)Re(CO)3(bzpy)+ Photophysics

Steady-state emission spectroscopy and emission quantum yields. Corrected

steady-state emission spectra were recorded on degassed acetonitrile solutions of each

complex with a SPEX F-l 12 fluorimeter. Samples were contained in 1 cm x 1 cm quartz

cuvettes and excited at 350 nm. Emission quantum yields (Dem) were calculated relative

to two actinometers using (2-17).95

(xem ) (11,,Pr J ,D (2-17)


In (2-17), x represents properties of the unknown solution and r represents properties of

the actinometer, A is the sample solution absorbance at the excitation wavelength, T1 is

the sample solvent refractive index, and D is the area under the emission band. Rul(bpy)3

in degassed water ((I)em = 0.055)96 and 9,10-dicyanoanthracene in ethanol ((Dem = 0.89)97

were used as actinometers. All solution concentrations were adjusted to result in

optically dilute solutions (A350 nm = 0.14).

Emission Lifetimes. Time-correlated single-photon counting (FLI,

Photochemical Research Associates) was used to measure emission lifetimes. The

excitation and emission wavelengths were selected with bandpass filters (excitation,

Schott UG-11 (350 nm maximum); emission, 550 nm interference filter). Degassed

acetonitrile samples were contained in 1 cm x 1 cm quartz cuvettes. Lifetimes were

calculated from single-exponential fits with the DECAN fluorescence lifetime

deconvolution software.98

LIOAS Measurements. LIOAS measurements were conducted on acetonitrile

samples with the apparatus described above. Before each experimental run, a linearity








test was performed with the ferrocene reference to determine the maximum usable laser

energy while maintaining linearity. Based on these tests, laser energies of 2 and 20 pJ

pulse'l were used for the 1 and 5 MHz transducers, respectively. Four experimental

cycles were performed for each compound and averaged, with each cycle consisting of

fresh ferrocene reference solution and (b)Re'(CO)3(bzpy) solution measurements. Each

measurement was the average of acoustic waveforms collected from 1000 laser pulses at

a 10 Hz repetition rate. All samples were nitrogen degassed in the fixed LIOAS cell for

20 minutes before data acquisition.

Deconvolution analysis was performed with the two-component sequential step

model. Lifetimes for the fast decay component were fixed at 10 and 1 ns for the 1 MHz

and 5 MHz transducers, respectively, while the other fit parameters were allowed to float.

For the 1 MHz transducer data, only a background correction was necessary to achieve

the desired fit, but the narrower bandwidth of the 5 MHz transducer data required both

background and reference shift correction factors in the final deconvolution process.













5-5' BIPHENYL OLIGOMER PHOTOPHYSICS


Introduction


As discussed earlier, a series of oligomers (5-L series) was synthesized containing

biphenyl subunits in the conjugated backbone. The oligomers contain a 5,5'-(2,2'-

bipyridyl) core with primary repeat units on either side consisting of 5,5'-diethynyl(2,2'-

biphenyl) and dialkoxybenzenes. These oligomers were synthesized via Sonogashira

coupling, an iterative sequence involving palladium-mediated cross coupling of a

terminal acetylene and aryl iodide.64'99 Complexes were synthesized by lighting these

oligomers to the -ReI(CO)3CI (5-Re series)99'100 and -ReI(CO)3(NCCH3)+ (5-ReAN-2

and 5-ReAN-3 complexes) chromophores. The structures of the 5-L oligomers and 5-Re

complexes are shown in Figure 3-1. Extensive photophysical and photothermal studies

were conducted on these molecules, and the results are presented in this chapter.

Results


Various photophysical parameters from many different measurements are

presented for the uncomplexed 5-L oligomers and 5-Re rhenium complexes in Tables 3-1

and 3-2, respectively. The individual measurements are discussed below. For

comparative purposes, some of the photophysical data collected for polymers PI and P4

described in chapter 1 (Figure 1-15) are also presented.









OMe OMe
'*' '-N N -
OMe OMe
5-L-1: M = -
5-Re-1: M = Re'(CO)3CI
OR OR
-- /---- -
~-N N- -
RO M RO
5-L-2: M =-
5-Re-2: M = Re'(CO)3CI
5-ReAN-2: M = Re'(CO)3(NCCH3)+OTf-
OM. OR OR OMe
---N-~--N --'- -'
MeO RO RO Ols
5-L-3: M = -
5-Re-3: M = Re'(CO)3CI
5-ReAN-3: M = Re'(CO)3(NCCH3)+OTf
OMe OR OR OR OR OMe
---a-,." -a '' ;=;- ,.-.., -" :.N =,------"-- -- -'--- ;- -="" --
MeO RO RO V' RO OR OMe
5-L-4: M = -
5-Re-4: M = Re'(CO)3CI
R = C18H37


Figure 3-1: 5-L oligomer and 5-Re rhenium complex structures.





Table 3-1: 5-L oligomer photophysics.

1 5-L-1 5-L-2 5-L-3 5-L-4

Absorption X./nm 330(3.85) 320(6.90) 340(9.05) 336(15.2)
(Fa/ 104 Ml cm') 370(5.40) 400(9.80) 404(13.5) 406(25.1)

Emission 298 K / n 455 454 453 452

o80 K/nm 413 469 482 496

*em 0.89 0.72 0.68 0.79

TA T298K/tS 158 452 343 411

Note: Measurements were conducted on argon bubble-degassed THF solutions. Additional experimental
conditions are discussed in the text.











Table 3-2: 5-Re rhenium complex photophysics.


I 5-Re-1


5-Re-2


5-Re-3


Xmnx/nm
(E~a / 104 Mr cmu )


Xmax, 298 K / nll
X.., 0K / nm

T298 K / ns


332(2.90) 336(8.30) 352(11.8) 338(16.8)
410(3.40) 440(7.34) 444(8.30) 388(20.7)

444 (10.3)
690 650 652 650


659
145


Electrochem


E12d / V vs.SCE


-0.90b -0.92b -0.85bc
Note: Measurements were conducted on argon bubble-degassed THF solutions. Additional experimental
conditions are discussed in the text. aPt disc working electrode. bGCE disc working electrode. 'Irreversible
reduction.


Absorption


Emission


/o1/nm
(emax / 104 M"' cm"')


a,298 K/ nm
max., 80oK / nm

T298 K / ns


5-ReAN-2

340 (9.49)
449 (7.38)
652

589,625


9710


5-ReAN-3

348 (14.7)
447 (9.49)
650


629

5010


Note: Measurements were conducted on argon bubble-degassed THF solutions (except for transient
absorption measurements, which are conducted in methylene chloride). Additional experimental conditions
are discussed in the text.


Absorption Spectra

Absorption spectra were obtained on dilute THF solutions of the various

oligomers and rhenium complexes, and molar absorptivity values (c, M'1 cm'1) were

calculated based on (3-1).


A= sbc


Absorption


Emission


5-Re-4


-0.89a


-0.87a


-0.86 a


_0.91Iac


(3-1)


I








In (3-1), A is the sample absorbance, b is the cell pathlength (1 cm), and c is the sample

concentration (M). Absorption spectra for the 5-L and 5-Re series, along with P1 and

P4, are shown in Figure 3-2. Absorptivity for P1 was calculated based upon the polymer

repeat unit. Absorptivity calculations were not performed on P4. Absorption maxima for

all oligomers and rhenium complexes are listed in Tables 3-1 and 3-2, respectively.

The oligomer spectra exhibit two 7t,7t* transitions, with the lower energy (HOMO

LUMO) transition corresponding to a long-axis polarized transition and the higher

energy transition corresponding to a perpendicular short-axis transition. The low-energy

band red-shifts to lower energies from 5-L-1 to 5-L-2. However, further shifting does not

readily occur as the oligomer size increases from 5-L-2 to 5-L-4. This observation

suggests that the effective conjugation length (i.e., oligomer "bandgap") is reached

relatively early in the series. Note the similarity in the 5-L-4 and P1 spectra, which are

similar to other reported PPE-type oligomer and polymer absorption spectra (Figure

1-4) .5,26,101-103 The oligomer bands are blue-shifted compared to PPE (Figure 1-4) due to

the incorporation of the bipyridine and biphenyl subunits, which is analogous to the

bipyridine-containing BEH-PPV blue-shift discussed in chapter 1.















E
0
40 E

CAT

20



0


350 400 450 500 550

Wavelength / nm


Figure 3-2: Absorption spectra in THF. (a) 5-L oligomers and P1; (b) 5-Re complexes
and P4; (c) 5-ReAN-2 and 5-ReAN-3 complexes.


00-
300








While the 5-Re rhenium complex spectra exhibit at least two similar 7,71*

transitions, a significant long-axis nt,7r* transition (HOMO -+ LUMO) red-shift and

smaller short-axis transition red-shift in comparison to the free oligomer spectra is

observed. The energy of the low-energy band remained fairly constant in the complexes,

while the high-energy band continues to red-shift with increasing oligomer length. This

feature suggests that for 5-Re-2 5-Re-4 the low-energy band is associated with a

"constant" chromophore, while the higher energy band arises from a separate "varying"

chromophore that is dependent on the oligomer length. The implications of this

observation are discussed later. Note that the molar absorptivities are considerably higher

than expected for any MLCT-based absorptions,104 so it is believed that these absorptions

are "buried" under the more intense oligomer 71,71* transitions. Also, the 5-Re-4 and P4

spectra are very similar, suggesting that the oligomers readily reflect the polymer

photophysics.

Emission Spectra

Emission spectra of the 5-L oligomers in optically dilute 2-methyltetrahydrofuran

(2-MTHF) solutions at temperatures ranging from room temperature to 80 K are shown in

Figure 3-3. Emission maxima at room temperature and 80 K are listed in Table 3-1. The

oligomer fluorescence spectra at room temperature feature a strong band that exhibits a

small Stokes shift (i.e., shift to lower energies) from the lowest-energy absorption. On

this basis, the emission is assigned to the long-axis polarized '%t,t* state. This

fluorescence is very similar in energy and bandshape to related PPE (Figure 1-4) and PPV

n-conjugated polymers and oligomers, including P1. 1,21'26'46,105-107 The fluorescence








maximum did not vary significantly throughout the oligomer series. Therefore, the 't,7r*

excited-state energy essentially remained constant upon variation of the oligomer length,

which mirrors the lack of variation in the lowest-energy absorption band maximum.

Comparison of the oligomer fluorescence spectra reveals that the spectral bandwidth

decreases with increasing oligomer length. In addition, a clear trend emerges for

oligomers 5-L-2 5-L-4 as the intensity of the (0,1) shoulder decreases relative to the

(0,0) maximum with increasing oligomer size. These observations signal that the

electron-vibration coupling in the 7r,7tr* state decreases with increasing oligomer length

due to greater 1n,71* state delocalization. This decrease suggests that the excited state is

less "distorted" upon photoexcitation, possibly due to the increased steric bulk of the

alkyl chains as the oligomer size increases. A similar fluorescence trend was observed by

Becker and coworkers for a series of oligothiophenes, and they suggested a similar

conclusion.29 No phosphorescence was detected at low temperatures for any of the 5-L

oligomers or P1. This observation for the polymers is not terribly surprising, as the

presence of defect sites or "exciton traps" would provide a nonradiative decay route,

consequently excluding the observation of phosphorescence.

The oligomer fluorescence red-shifted with decreasing temperature, and at the

lowest examined temperatures for all of the oligomers (except 5-L-1) the emission was

dominated by a broad band at a lower energy than the assigned room temperature (0,0)

band. A corresponding thermochromism was seen in the lowest-energy ,Ttt* absorption

band for 5-L-3 and 5-L-4 (data not shown). Excitation spectra for the oligomers

measured at different wavelengths on the emission band were generally indistinguishable,

suggesting that the states involved in the observed photophysics were in strong electronic






72

communication. Low temperature spectra of 5-L-1 show a dramatic blue-shift below 110

K leading to a final structured spectra after exhibiting the red-shift seen in all other

oligomers at higher temperatures.


400 450 500 550 600
Wavelength / nm


Figure 3-3: Emission spectra of the 5-L oligomers in 2-MTHF (350 nm excitation) at
temperatures varying from 298 to 80 K. Emission intensity decreases as temperature
decreases, and spectra are in 20 K increments. (a) 5-L-1 (note unusual low-temperature
trends); (b) 5-L-2; (c) 5-L-3; (d) 5-L-4.








Emission quantum yields were measured for the oligomers using (2-17), and

calculated values are listed in Table 3-1. The high emission quantum yield is typical of

rigid-rod 7t-conjugated polymers and other rigid organic fluorophores.108 The quantum

yields decrease as the oligomer size increases (except 5-L-4), suggesting more efficient

intersystem crossing as the extended structure of the oligomer increases.

Polarized emission measurements were performed on oligomers 5-L-3 and 5-L-4

to further study the interesting thermochromism. Wavelength-resolved polarization

anisotropies (r(X)) were calculated with (3-2).109

r()= Ivv -GIvH (3-2a)
Ivv +2GIvH

G ='IHV
IHH (3-2b)

In (3-2), Ixy is the emission intensity with the excitation and emission polarizers adjusted

according to x and y, respectively (e.g., IHV is the emission intensity with horizontally

polarized excitation light and vertically polarized emission detection). Anisotropy

measures the polarized light component ratio to its total intensity and is a direct indication

of the angle between absorption and emission dipoles, a. Anisotropy values vary from

0.4 (a = 0) to -0.2 (a = 90), with an anisotropy value of zero statistically representing

unpolarized light (e.g., a uniform statistical distribution of emitting dipole angles relative

to the absorption dipole).109

Emission spectra at room temperature and 170 K in 2-MTHF and calculated

anisotropies at these temperatures are shown in Figure 3-4, and the anisotropy

temperature dependence at 525 nm for both oligomers is shown in Figure 3-5. The 170 K






74


experiment temperature is slightly above the 2-MTHF freezing point, thus eliminating

solvent glass effects on the observed anisotropy. At 298 K, r(,) is relatively constant

across the fluorescence band (r 0.24) for both oligomers. With decreasing temperature

r(X) slightly increases on the blue side of the fluorescence band, but a sharp decrease on

the far red side of the band is observed for 5-L-3 at T < 190 K and for 5-L-4 at T < 230

K. The implications of these observations are discussed below.



a. 0.5
r\ 4
S \ 0.4
0.3
0.2
0 \ .1
1: : ; F 0.0
b. 0.S
: / \0.4

S \ 0.3




0.
YN~w~V#v~ 0.1
l N m 0.01
S" /\ c. 0.5
|/ ,, 0.4
/ \ 0.3
0.3
0.2
/L 0.1
> I 1 I I II I r :'l 0.0
\ d. 0.5
: / ^ .0.4
I \ o03


/ 0.1
....... A 0 .0
400 450 500 550 600 650
Wavelength I nm


Figure 3-4: Emission (dashed line) and emission polarization (solid line) r(X) spectra
(350 nm excitation) in 2-MTHF. (a) 5-L-3,298 K; (b) 5-L-3,170 K; (c) 5-L-4,298 K;
(d) 5-L-4, 170 K.








0.30 .


0.25


W 0.20


0.15


0.10 .'
160 200 240 280
Temperature / K

Figure 3-5: Emission anisotropy temperature dependence observed at 525 nm. Solid
circles are 5-L-3 data, and open circles are 5-L-4 data.



Emission spectra for the 5-Re complexes in optically dilute 2-MTHF solutions at

temperatures ranging from 298 to 80 K are shown in Figure 3-6. Emission maxima at

298 and 80 K are listed in Table 3-2. Although not shown, a weak emission was

observed in all the rhenium complex samples that matched the free oligomer 't,7*

fluorescence seen in Figure 3-3. This emission is two orders of magnitude smaller than

those observed for the uncomplexed oligomers. It is impossible to know whether this

fluorescence originates from the rhenium complexes or is a trace oligomer impurity in the

rhenium complex samples. Nonetheless, it is clear that the oligomer fluorescence is

strongly quenched by the MLCT chromophore.



















S" b. 5-Re-2 e. 5-ReAN-2-




.0
.2 II ;II' : I- I I :* I I E D a M :













500 550 600 650 700 750 500 550 600 650 700 750 800

Wavelength / nm

Figure 3-6: Emission spectra of the 5-Re complexes in 2-MTHF (440 nm excitation) at
various temperatures from 298 to 80 K. Emission intensity increases with decreasing
temperature, and spectra are in 20 K increments. (a) 5-Re-1; (b) 5-Re-2; (c) 5-Re-3; (d)
Ii.

a,

C



















5-Re-4; (e) 5-ReAN-2; (f) 5-ReAN-3.
E






500 550 600 650 700 750 500 550 600 650 700 750 800

Wavelength / nm

Figure 3-6: Emission spectra of the 5-Re complexes in 2-MTHF (440 nim excitation) at
various temperatures from 298 to 80 K. Emission intensity increases with decreasing
temperature, and spectra are in 20 K increments. (a) 5-Re-i; (b) 5-Re-2; (c) 5-Re-3; (d)
5-Re-4; (e) 5-ReAN-2; (f) 5-ReAN-3.



The rhenium complexes exhibited a weak, low-energy emission that increased

with decreasing temperature (about twenty-fold from 298 to 80 K). Spectra for 5-Re-1

evolved from a broad structureless 680 nm band at 298 K to a blue-shifted, highly

structured 586 nm band at 80 K. This thermally-induced emission energy shift exhibits

trends typically observed for (b)Rel(CO)3C1 3MLCT emission.41 For the remaining








rhenium complexes, a 650 nm band was observed at 298 K with a poorly defined vibronic

structure, and a superposition of a structureless 600 nm band and a structured (0,0) 650

nm band with a vibronic (0,1) shoulder was obtained at 80 K. In general, there was very

little band shifting of the structured emission to higher or lower energies as the

temperature decreased for these complexes, and the observed band superposition "blurs"

as the oligomer size increases. Attempts to measure the luminescence quantum yields of

the 5-Re complexes were unsuccessful, as in each case the emission was too weak to be

effectively measured (Iem < 10-4). Excitation spectra probing this emission (not shown)

agree well with the absorption spectra, suggesting efficient electronic communication

between the 7,7r* oligomer and dn (Re) -> n* MLCT excited states.

In order to further probe the superimposed emission spectra at low temperatures,

excitation polarization studies were conducted at 80 K on 2-MTHF solutions of 5-Re-3

using various emission wavelengths. Excitation spectra and r(X) values are shown in

Figure 3-7 along with an 80 K emission spectrum that indicates the examined

wavelengths. For the blue structureless shoulder of the emission spectrum, the anisotropy

value is high for the lowest-energy absorption band (0.3), which strongly suggests that the

absorbing and emitting states are the same (i.e., little electronic rearrangement occurs

between the absorbing and emitting states). As expected, the anisotropy value drops as

the excitation wavelength decreases, since the absorbing state is now a higher-energy

excited state than the emitting state. The excited complex must undergo internal

conversion in this situation to reach the emitting state, which would certainly change the

transition dipole and, consequently, the observed anisotropy.109 The anisotropies

recorded at the maximum of the structured emission shows a lower anisotropy value (0.1)





78

that does not vary across the excitation spectrum. This observation that the anisotropy is

nearly zero (i.e., the emission is almost completely unpolarized) and independent of

excitation wavelength is common when phosphorescence from a triplet excited state is

observed, since this state is typically very delocalized in the photoexcited

chromophore. 109-111










S 550 600 650 700 750 800

.0 OA


C
| ; : 0.2

0
I | \ o .1
0 Excitation (Xom = 585 nm) 0.0
,,, / 0.4

/ \ 0.3
/ \-- \r 0.2
\ 0.1

Excitation ([m = 655 nm) 0.0
300 350 400 450 500 550
Wavelength / nm


Figure 3-7: Excitation (dashed line) and excitation polarization (solid line) r(,) spectra at
80 K of 5-Re-3 2-MTHF solution at various emission wavelengths.








Based on the polarization data, the structured emission observed at low

temperatures is 3n7,7t* phosphorescence originating from the completed oligomer, while

the overlapping structureless emission that retains anisotropy is the MLCT emission after

undergoing an expected blue-shift from its room temperature position. Note, however,

that the phosphorescence anisotropy does not equal zero, indicating that some mixing of

phosphorescence and metal-based 3MLCT emission still occurs at low temperature.

Furthermore, the 3MLCT emission band wavelength is close to the 5-Re-1 80 K emission

maximum, further confirming its assignment. The presence of phosphorescence at lower

temperatures is likely due to nonradiative decay pathway restriction after the sample is

frozen in a glass. Similar overlapping MLCT and ligand emissions were reported by

Schmehl and coworkers in a rhenium complex with a styryl-substituted bipyridine ligand.

Low-temperature emission spectra of this complex exhibited overlapping metal-centered

and ligand-centered luminescence with differing lifetimes.112 The smaller oligomer

present in 5-Re-i evidently lacks the electron delocalization necessary to achieve the

"mixed-state" emission observed for the larger oligomers, since only 3MLCT emission is

observed.

One of the purposes for synthesizing the 5-ReAN complexes was to increase the

emission quantum yield and shift the MLCT emission away from the observed ligand

phosphorescence at low temperatures. Ligand substitution on (bpy)Rel(CO)3Cl to form

(bpy)ReI(CO)3(NCCH3)+ resulted in a 3MLCT emission maximum blue-shift of nearly

100 nm (from 642 to 540 nm), 3MLCT lifetime increase (from 150 to 1100 ns) and

emission quantum yield increase by two orders of magnitude (from 0.003 to 0.22).41'42

However, emission maxima of the 5-ReAN complexes are very similar to the








corresponding 5-Re molecules. The 80 K 3MLCT emission portion of the overlapping

spectrum is more prominent and slightly blue-shifted (around 575 nm) with respect to the

5-Re complexes, which might reflect the different chromophore excited state manifold

and potentially higher quantum yield relative to the 3 T,n* phosphorescence resulting from

ligand substitution. Furthermore, room temperature quantum yield measurements on

5-ReAN-2 and 5-ReAN-3 remained very low (< 0.005), which is surprising. The

implications of these observations are presented below.

Emission Lifetimes

Emission decay lifetimes were recorded for the 5-L oligomers in 2-MTHF at

various temperatures and emission wavelengths. Both monoexponential and

biexponential decays were observed, and lifetime results are listed in Table 3-3.

Biexponential fits were performed using (3-3), yielding decay times (Ti) and normalized

amplitudes (ai).


I(t)= oaI exp{t} + a2 exp{t} (3-3)


The room temperature lifetime of the oligomer 7,7* fluorescence generally

decreases with increasing oligomer size. On the blue side of the fluorescence band (450

nm), the fluorescence decay kinetics are single exponential at all temperatures (except

5-L-2). By contrast, on the low energy side of the fluorescence band (550 nm) the decays

become biexponential as the temperature decreases, featuring a long-lived component that

increases in amplitude with decreasing temperature. For 5-L-l, room temperature

biexponential decays are observed with little exhibited temperature dependence.

Although the amplitude of the long-lived component is small (< 0.04), the decay time is









significant, suggesting that at low temperatures this component substantially contributes

to the total emission yield."3 Note that the abrupt change in r(,) for both 5-L-3 (180 K)

and 5-L-4 (220 K) occurs at the same temperature where the emission decay kinetics

become biexponential.



Table 3-3: Variable temperature emission decay times of the 5-L oligomers.

450 nm Emission 550 nm Emission
Oligomer T / K cI T, / ps a2 T2 ps a, 1 T / ps a2 T2 / ps

5-L-1 298 1 2215 0.986 2143 0.014 7935
80 1 1335 0.985 1384 0.015 8007
5-L-2 298 1 1124 1 1129 -
80 0.964 870 0.036 4067 0.954 0971 0.046 5093
5-L-3 298 1 952.2 1 1021.1 -
270 1 969.4 1 1059.3 -
230 1 1031.5 1 1218.5 -
200 1 979.3 1 1234.5 -
180 1 945.9 0.974 1535.8 0.026 8049.9
5-L-4 298 1 770.8 1 829.2 -
270 1 719.3 1 822.9
230 1 737.2 1 1054.0 -
220 1 493.6 0.992 1436.7 0.008 9287.5
210 1 434.3 0.991 1401.1 0.009 8785.6
190 1 458.3 0.992 1435.6 0.008 9350.0
'2-MTHF solutions; 350 or 405 nm excitation. Biexponential fits were performed with (3-3). Errors for the
fit parameters are 5%.



Emission decay lifetimes were recorded for the 5-Re complexes in 2-MTHF at

various temperatures, and lifetime results are listed in Table 3-4. At all temperatures, the

emission decays were biexponential and generally characterized by a large amplitude,

short-lived component (T 1 ns, a > 0.95) and a low amplitude component with a









considerably longer lifetime (t 20 200 ns, a < 0.05). The short-lived component

shows little temperature dependence, but the long-lived component increases from a few

hundred nanoseconds to several microseconds as temperature decreases. Note that the

short-lived component amplitude for 5-Re-2 5-Re-4 increases with increasing oligomer

size. Considering the fit error, the long-lived room temperature lifetimes (except 5-Re-l)

are equivalent.



Table 3-4: Variable temperature emission decay times of the 5-Re complexes.

Complex Temp. / K ai T, / ns a2 T2 I ns

5-Re-1 280 0.927 1.598 0.073 14.1
171 0.996 1.951 0.004 204
81 0.528 60.8 0.472 6237
5-Re-2 280 0.987 1.969 0.013 153.6
170 0.999 0.831 0.001 843.8
82 0.999 2.39 0.001 2489
5-Re-3 298 0.994 2.36 0.006 174
169 0.999 2.05 0.001 2430
82 0.999 5.12 0.001 5107
5-Re-4 298 0.991 3.834 0.009 170.5
80 0.999 7.753 0.001 7608
5-ReAN-2 298 0.998 0.182 0.002 8.506
170 0.995 0.389 0.005 6.363
80 0.993 0.362 0.007 5.733
5-ReAN-3 298 0.997 0.165 0.003 9.250
170 0.992 0.507 0.008 6.852
80 0.991 0.321 0.009 5.705
'2-MTHF solutions, 350 or 405 nm Excitation. Decays were recorded at 600 nm. Biexponential decay fits
were calculated based on (3-3).








Exhaustive studies of emission decays at various temperatures and emission

wavelengths were performed on all rhenium complexes, and representative data for

5-Re-2 are shown in Figure 3-8. Similar data sets were observed for the other rhenium

complexes. On the blue side of the emission (600 nm), the short-lived component

dominates the emission decay. The longer-lived component increases in amplitude as the

emission wavelength increases. For all wavelengths (as also seen in Table 3-4 for 600

nm), the longer-lived component amplitude decreases with decreasing temperature,

rendering the component relatively indistinguishable from the baseline at temperatures

less than 220 K. This data is further discussed below.

As described above, the low temperature emission for these complexes is believed

to be overlapping MLCT emission and oligomer 37Ti* phosphorescence. Typically,

phosphorescence lifetimes are very long (tens to hundreds of microseconds). Clearly

these lifetimes were not observed in this data, which might indicate configurational

mixing of the two excited states. The increasing long-lifetime amplitude with increasing

emission wavelength suggests a greater contribution from the longer-lived oligomer 3n,tr*

phosphorescence for these wavelengths, which agrees with the excitation polarization

data.

It is worth noting that the 5-ReAN complexes have short lifetimes for each of the

decay components that are temperature independent, unlike the other rhenium complexes.

Again, this is counter to the expected photophysical trends for acetonitrile-substituted

complexes as described above.




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,' -4+4


PHOTOPHYSICAL STUDIES OF PI-CONJUGATED OLIGOMERS AND
POLYMERS THAT INCORPORATE INORGANIC MLCT CHROMOPHORES
By
KEITH A. WALTERS
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
2000

To the brave warrior in all of us...

ACKNOWLEDGMENTS
When you reach this point in your academic career, it is hard to go through and
thank all the individual people who guided you along the long path. First, I must thank
my parents for giving me the freedom to explore the wonderful world of life without
having the script already written for me. I also appreciated their patience when I opted
out of my initial career choice (medical school), decided to journey to Florida for
graduate school, and became a Methodist!
My desires to be a teacher (aside from the teaching experiences of my own
parents) come from two people. David Stamey, a history teacher in high school, made the
comment to me one day that I had better be a teacher or he would "hunt me down." At
the time I had problems understanding this compliment, but I can definitely tell Mr.
Stamey to put his gun away! The initial desire to teach was planted in his classes, but it
took my own experiences as a teaching assistant at Furman to spawn its full fruition. My
undergraduate advisor, mentor, and friend, Dr. Noel A.P. “crazy Australian”
Kane-Maguire, had a big hand in opening my eyes (color blind as they are) to the world
of photochemistry. Indeed, the entire chemistry department at Furman should be thanked
for their willingness to educate with the intensity and zeal they presented day after day.
I am firmly convinced that a student's experience in graduate school largely rests
in the hands of his or her graduate advisor. I am thankful to have been blessed with an
advisor that made it an amazing experience, Dr. Kirk Schanze. Kirk was always willing

to treat me as a colleague rather than a subordinate, and that works wonders on one's
creativity and initiative. I always appreciated his words of encouragement, his unique
ideas to try next, and his patience to let me try some things that probably would have
never worked out no matter what I did. Kirk gave me the freedom to learn and grow as
my own mind evolved, and that is probably the best gift any advisor can give.
Many people in Gainesville have made it a very good home for me. My fellow
group members (Joanne, Benjamin, Ed, Carla, Kevin, Yiting, Ben, Brian, Wang, Hai-
Feng) are all wonderful collaborators, willing to discuss problems and able to synthesize
those darned compounds that elude me! I look forward to seeing each and every one of
them prosper in their own professional and personal lives. The collaborations within the
department (especially with Dr. Dan Talham and Dr. Aiping Wu for the LB film work)
are always top notch. Outside of UF, my handbell choir at Trinity (Kathy, Keith [the
other one!], Andrew, Mark and Kristen, Quenta and Dana, Connie, Judy, Susan, Cheryl,
Dori, Nick, Jackie, Anna, Neil, and Rose) always brought a smile to my face, put a song
in my heart, and reminded me that other things do go on outside of a chemistry lab.
I have many collaborators outside of UF that have expanded the girth of my
understanding and appreciation of the world of chemistry. These include Dr. Stephan
Guillerez and Lise Trouillet at CEA-Grenoble, Dr. Hans van Willigen and Dr. Alejandro
Bussandri at the University of Massachusetts at Boston, Dr. Linda Peteanu and Lavanya
Premvardhan at Carnegie Mellon University, and Dr. Robert Pilato and Dr. Kelly Van
Houten at the University of Maryland.
IV

Lastly, I thank God for giving me the gifts to do what I do and the initiative to
actually use the gifts once I discover them. With His blessing, I pray that my life will
continue to grow and prosper both inside and outside of the chemistry lab.
v

TABLE OF CONTENTS
page
ACKNOWLEDGMENTS iii
LIST OF TABLES ix
LIST OF FIGURES xi
ABSTRACT xvi
u-CONJUGATED POLYMERS 1
Introduction 1
Phenylenevinylene- and Aryleneethynylene-Based Polymers 1
Polythiophene-Based Polymers 7
MLCT-Incorporated ^-Conjugated Polymers 12
Phenylenevinylene- and Aryleneethynylene-Based Polymers 12
Polythiophene-Based Polymers 18
Previous Group Work 20
Scope of This Work 22
PHOTOTHERMAL CHEMISTRY 24
Theory 25
Time-Resolved Thermal Lensing 25
The thermal lens theory 26
A simplified calculation method 29
Limitations and instrumental considerations 32
Photoacoustic/Laser-Induced Optoacoustic Spectroscopy 35
Early photoacoustic techniques 37
Laser-induced optoacoustic spectroscopy 38
Accounting for solution volume changes 41
Instrument Design and Calibration Studies 43
Time-Resolved Thermal Lensing 43
Apparatus setup 43
Calibration studies 45
Laser-Induced Optoacoustic Spectroscopy 48
Apparatus setup 48
Calibration study - (b)Re'(CO)3(bzpy)+ triplet energies 50
Experimental 60
vi

(b)Re'(C0)3(bzpy)+ Synthesis 60
(b)Re(CO)3(bzpy)+ Photophysics 63
5-5' BIPHENYL OLIGOMER PHOTOPHYSICS 65
Introduction 65
Results 65
Absorption Spectra 67
Emission Spectra 70
Emission Lifetimes 80
Transient Absorption Spectra 84
Photothermal Measurements 89
Transient Absorption Quenching / Oligomer Triplet Energy 91
Decay Rate Calculations 93
Excited-State Energy Transfer 96
Langmuir-Blodgett Films 98
Electrochemistry 106
Discussion 106
Oligomer Ligand Conformation 106
Electronic absorption spectra 108
Emission spectra 109
Oligomer triplet energies 110
Oligomer Temperature Dependence and Aggregation 111
Excited State Photophysics of the Rhenium Complexes 115
Experimental 122
Oligomer and Complex Synthesis 122
Photophysical Measurements 123
Electrochemical Measurements 124
Langmuir-Blodgett Film Preparation 125
5-5' MONOPHENYL OLIGOMER PHOTOPHYSICS 126
Introduction 126
Results 126
Absorption Spectra 128
Emission Spectra 129
Emission Lifetimes 135
Transient Absorption Spectra 138
Electrochemistry 140
Discussion 140
Experimental 145
Oligomer and Complex Synthesis 145
Photophysical Measurements 146
Electrochemical Measurements 146
Vll

4,4' OLIGOMER PHOTOPHYSICS
147
Introduction 147
Results 147
Absorption Spectra 149
Emission Spectra 151
Emission Lifetimes 157
Transient Absorption Spectra 161
Photothermal Measurements / Triplet Yields 165
Decay Rate Calculations 167
Electrochemistry 169
Electroabsorption Spectroscopy 169
Discussion 172
Excited-State Energetics 172
How Does the Substitution Position Alter the Photophysics? 174
Semi-Empirical Calculations 177
Mulliken Theory Calculation of 4-Re-l MLCT Dipole Moment 182
Experimental 189
Oligomer and Complex Synthesis 189
Photophysical Measurements 189
Electrochemical Measurements 190
Semi-Empirical Calculations 190
THIOPHENE PHOTOPHYSICS 191
Introduction 191
Results 193
Electrochemistry 194
Absorption Spectra 197
Emission Spectra and Decay Kinetics 202
Transient Absorption Spectra 210
Discussion 218
Excited-State Energetics 218
Electron Transfer Energetics 220
Implications of this Work 227
Experimental 229
Model Complex and Polymer Synthesis 229
Photophysical Measurements 229
Electrochemical Measurements 230
CONCLUSIONS 231
REFERENCES 235
viii
BIOGRAPHICAL SKETCH
251

LIST OF TABLES
Table page
2-1. Emission data for (b)Re'(CO)3(bzpy)+ 53
2-2. LIOAS data for (b)Re'(CO)3(bzpy)+ 58
3-1. 5-L oligomer photophysics 66
3-2. 5-Re rhenium complex photophysics 67
3-3. Variable temperature emission decay times of the 5-L oligomers 81
3-4. Variable temperature emission decay times of the 5-Re complexes 82
3-5. 5-L oligomer LIOAS data 89
3-6. 5-Re complex LIOAS data 90
3-7. Triplet energies of the 5-Re complexes 90
3-8. 5-L oligomer and PI triplet quenching study results 91
3-9. Triplet photophysics of PI and 5-L oligomers 96
3-10. Decay rates of the 5-L oligomers 96
3-11. Fluorescence intensity ratios for mixed samples 98
3-12. Surface coverage calculations for mixed 5-L-3 / 5-Ru-2 LB films 104
4-1. 5-LP oligomer photophysics 127
4-2. 5-ReP rhenium complex photophysics 128
4-3. Variable temperature emission decay times of the 5-LP oligomers 136
4-4. Variable temperature emission decay times of the 5-ReP complexes 137
5-1. 4-L oligomer photophysics 149
5-2. 4-Re rhenium complex photophysics 149
IX

159
5-3. Variable temperature emission decay times of the 4-L oligomers
5-4. Variable temperature emission decay times of the 4-Re complexes 160
5-5. 4-L oligomer LIOAS data 165
5-6. 4-Re complex LIOAS data 165
5-7. 4-L oligomer triplet yields 166
5-8. Triplet photophysics of the 4-Re complexes 167
5-9. Decay rates of the 4-L oligomers 168
5-10.2-SA, 3-SA and 4-SA photophysical data 175
5-11. Semi-empirical calculations for 5-M and 4-M 178
5-12. Semi-empirical calculations for 5-L-l and 4-L-l 180
5-13. Singlet ground state molecular orbitals for 5-M and 4-M 186
5-14. Singlet ground state molecular orbitals for 5-L-l and 4-L-l 187
5-15. Singlet ground state molecular orbitals for 5-L-1T and 4-L-1T 188
6-1. Thiophene model complex photophysics 194
6-2. Thiophene polymer photophysics 194
6-3. Electrochemistry of thiophene complexes and polymers 197
6-4. Franck-Condon emission bandshape fitting parameters for model complexes 203
6-5. Electron transfer rate constants for thiophene-bipyridine models and polymers....221
6-6. Electron transfer free energy changes for thiophene-bipyridine models and
polymers 225
x

LIST OF FIGURES
Figure page
1-1. BEH-PPV and 2,2’-bipyridine-containing BEH-PPV 2
1-2. 2,2’-Bipyridine-containing PPV singlet excited-state difference absorption
spectrum in toluene 3
1 -3. Aryleneethynylene-based polymer structure 4
1-4. PPE absorption (solid line) and emission (dashed line) spectra in chloroform 4
1-5. Anthracene-containing aryleneethynylene polymer 5
1-6. Absorption (solid line) and emission (dashed line) spectra in chloroform of the
polymer in Figure 1-5 with x = 0.17 6
1-7. Cyclophane-containing aryleneethynylene polymer 6
1-8. Absorption (in dioxane) and triplet-triplet absorption difference spectra (in
benzene, 347 nm excitation) of an oligo(thiophene) series 9
1 -9. Cyclophane-containing polythiophene polymer 10
1-10. Poly(3-alkylthiophene) repeat structures 10
1-11. Poly-2,2’-bipyridine ruthenium-containing polymer 13
1-12. Aryleneethylylene-based polymers containing platinum subunits 14
1-13. Ru(bpy)32+-containing PPV polymer 15
1-14. Conformation change upon metal complexation 16
1-15. Ruthenium-containing diazabutadiene polymer 17
1-16. PPV-type polymer with tethered ruthenium chromophores 18
1-17. Ru(bpy)32+-substituted polythiophene 18
1-18. Metallorotaxane-thiophene polymers 19
xi

1-19. SALOTH thiophene polymer 20
1-20. Aryleneethynylene polymers containing (bpy)Re’(CO)3Cl 21
2-1. Basic TRTL longitudinal apparatus 25
2-2. Thermal lens Gaussian probe beam divergence 27
2-3. TRTL spectrum of phthalazine in benzene 30
2-4. Time-resolved pulsed thermal lens signal obtained for 10° M erythosine in water .33
2-5. TRTL apparatus with probe beam absorption compensation 35
2-6. Basic photoacoustic experimental setup 36
2-7. Typical photoacoustic response 37
2-8. Photoacoustic calibration plots 39
2-9. Simulated transducer responses based on (2-11) with varying x values as
indicated, where u = 1 x 106 Hz and to = 1 ms 40
2-10. TRTL apparatus layout 45
2-11. Ruthenium / viologen donor-acceptor system 47
2-12. LIOAS apparatus layout 49
2-13. LIOAS apparatus images 51
2-14. (b)Re(CO)3(bzpy)+ complexes 52
2-15. LIOAS data (signal vs. time) for (b)Re(CO)3(bzpy)+ in acetonitrile 55
2-16. Corrected emission spectra of (b)Re'(CO)3(bzpy)+ in acetonitrile solution at
298 K 59
3-1. 5-L oligomer and 5-Re rhenium complex structures 66
3-2. Absorption spectra in THF. (a) 5-L oligomers and PI; (b) 5-Re complexes and
P4; (c) 5-ReAN-2 and 5-ReAN-3 complexes 69
3-3. Emission spectra of the 5-L oligomers in 2-MTHF (350 nm excitation) at
temperatures varying from 298 to 80 K 72
xii

3-4. Emission (dashed line) and emission polarization (solid line) r(X) spectra (350 nm
excitation) in 2-MTHF. (a) 5-L-3, 298 K; (b) 5-L-3, 170 K; (c) 5-L-4, 298 K;
(d) 5-L-4, 170 K 74
3-5. Emission anisotropy temperature dependence observed at 525 nm. Solid circles
are 5-L-3 data, and open circles are 5-L-4 data 75
3-6. Emission spectra of the 5-Re complexes in 2-MTHF (440 nm excitation) at
various temperatures from 298 to 80 K 76
3-7. Excitation (dashed line) and excitation polarization (solid line) r(A.) spectra at
80 K of 5-Re-3 2-MTHF solution at various emission wavelengths 78
3-8. Normalized emission decays (intensity versus time) of 5-Re-2 at various
emission wavelengths and temperatures 84
3-9. Transient absorption spectra of the 5-L oligomers in freeze-pump-thaw degassed
THF solutions 87
3-10. Transient absorption spectra of the 5-Re complexes in argon bubble-degassed
THF solutions (except for 5-ReAN-2 and 5-ReAN-3, which are in CH2CI2) 88
3-11. Sandros energy-transfer quenching plots (log (kq) versus acceptor energy) 95
3-12. Emission spectra of a 1:1 mixture of 5-L-3 and 5-Re-3 (2 x 10'6 M) in 2-MTHF
at various temperatures ranging from 298 to 80 K in 20 K increments 97
3-13. Photophysics of 5-Ru-2 Langmuir-Blodgett films 101
3-14. Pressure isotherms of Langmuir-Blodgett films of 5-L-3 / 5-Ru-2 mixtures 103
3-15. Photophysics of 5-L-3 / 5-Ru-2 mixed Langmuir-Blodgett films 105
3-16. Effect of metal complexation to the conjugated segments of the oligomer 108
3-17. Proposed oligomer aggregation mechanism 115
3-18. Jablonski diagram of 5-Re excited state energy levels 116
3-19. Transient EPR spectra of 5-L-l (biphenyl analogue, dotted line) and 5-ReAN-2
(solid line) at 130 K in 1:1 toluenexhloroform solution 119
3-20. Luminescence decays of [(bpy)2Ru(bpy_pyr)]2+ in 4:1 EtOH:MeOH at various
temperatures 121
4-1. 5-LP oligomer and 5-ReP rhenium complex structures 127
4-2. Absorbance spectra in THF. (a) 5-LP oligomers; (b) 5-ReP complexes 130
xiii

4-3. Emission spectra of the 5-LP oligomers in 2-MTHF (360 nm excitation) at
various temperatures ranging from 298 to 80 K 131
4-4. Emission spectra of the 5-ReP complexes in 2-MTHF (450 nm excitation) at
various temperatures ranging from 298 to 80 K 134
4-5. Excitation (dashed line) and excitation polarization (solid line) r(X) spectra at
80 K of 2-MTHF 5-ReP-3 solution at various emission wavelengths 135
4-6. Transient absorption spectra of the 5-LP oligomers in freeze-pump-thaw
degassed THF solutions 141
4-7. Transient absorption spectra of the 5-ReP complexes in argon bubble-degassed
THF solutions 142
5-1. 4-L oligomer and 4-Re complex structures 148
5-2. Absorption spectra in THF. (a) 4-L oligomers; (b) 4-Re complexes 150
5-3. Fluorescence spectra of the 4-L oligomers in 2-MTHF (350 nm excitation) at
temperatures varying from 298 to 80 K 152
5-4. Emission spectra of the 4-Re rhenium complexes in 2-MTHF (400 nm
excitation) from 298 to 80 K 155
5-5. Excitation (dashed line) and excitation polarization (solid line) r(X) spectra at
80 K of 4-Re-3 2-MTHF solution at various emission wavelengths 158
5-6. Transient absorption spectra of the 4-L oligomers in freeze-pump-thaw
degassed THF solutions 162
5-7. Transient absorption spectra of the 4-Re rhenium complexes in argon
bubble-degassed THF solutions (except 4-ReAN-3, which is in CH2CI2) 164
5-8. Electroabsorption spectroscopy of 4-Re-l in a PMMA matrix at 80 K 172
5-9. Jablonski diagram of 4-Re complexes 173
5-10. Stilbazole-containing complexes 175
5-11. “Linear” and “bent” PPE-type polymers 177
5-12. Arylethynylpyridine model compounds 178
5-13.4-Re-l calculated LUMO molecular orbital 184
6-1. Thiophene model complex and polymer structures 193
xiv

198
6-2. Cyclic voltammetry in CH3CN solution / 0.1 M TBAH, with a Pt working
electrode, Pt auxiliary electrode, and Ag/Ag+ (10'2 M) reference electrode.
(a) [Os(bpy)3][PF6]2; (b) P4-Os; (c) P4-Ru; (d) [Ru(bpy)3]Cl2
6-3. Thiophene model complex and polymer absorption spectra in acetronitrile
solutions (except P4, which is in THF) 199
6-4. Thiophene model complex emission spectra in acetonitrile (380 nm excitation) ..203
6-5. Thiophene polymer emission (solid line) and excitation (dashed line) spectra in
optically dilute acetonitrile solution (except P4, which is in THF solution) 209
6-6. Transient absorption spectra of Ru(tpbpy)(bpy)22+ in acetonitrile 211
6-7. Transient absorption spectra of Ru(tpbpy)32+ in acetonitrile 212
6-8. Transient absorption spectra of P4 in argon bubble-degassed THF 214
6-9. Transient absorption spectra of P4-Ru in acetonitrile 215
6-10. Transient absorption spectra of P6-Ru in acetonitrile 216
6-11. Transient absorption spectra of P4-Os in acetonitrile 217
6-12. Thiophene-bipyridine polymer Jablonski diagram 218
6-13. Photoinduced electron transfer process from M(P4bpy)(bpy)22+ to MV2+ 227
xv

Abstract of Thesis Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
PHOTOPHYSICAL STUDIES OF PI-CONJUGATED OLIGOMERS AND
POLYMERS THAT INCORPORATE INORGANIC MLCT CHROMOPHORES
By
Keith A. Walters
August, 2000
Chairman: Kirk S. Schanze
Major Department: Chemistry
The use of ^-conjugated polymers in various material devices has encouraged
increased research interest in their photophysical properties in recent years. The
integration of transition metal chromophores with metal-to-ligand charge transfer
(MLCT) excited states into the polymers permits easy variation of the polymer excited-
state properties, since the MLCT chromophore redox potentials are tunable via ligand
variation. With this design consideration in mind, the photophysics of two different types
of metal-organic polymers are presented.
First, a series of PPE-type aryleneethynylene oligomers containing a 2,2’-bipyridyl
unit for transition metal coordination are considered. The oligomers have a well-defined
repeat structure, unlike polymers previously studied in our group with the same subunits
that exhibited unusual photophysical behavior. These oligomers are studied by
xvi

themselves and coordinated to -Re^CO^Cl and -ReI(CO)3(NCCH3)+OTr
chromophores. Second, a series of poly(3-alkylthiophene) polymers containing varying
amounts of 2,2’-bipyridyl subunits are synthesized and coordinated to -Ru"(2,2’-
bipyridine)22’ and -Osll(2,2’-bipyridine)22+ chromophores. The photophysical and
photothermal results of these two types of molecules are presented and interpreted,
paving the way for the design of better polymers for materials applications. Particular
attention is paid to the following:
The effect of oligomer and polymer coordination to the metal chromophore.
Upon coordination of the metal chromophore to the oligomer or polymer, the primary
absorption bands red-shift. Furthermore, organic-based fluorescence is quenched, giving
rise to an MLCT-based emission.
The effect of increasing the oligomer effective conjugation length. When the
conjugation length is increased by lengthening the oligomer, results show that anticipated
photophysical results are not obtained for the PPE-type oligomers, suggesting conjugation
breaks in the oligomer backbone via geometric twisting.
The observed excited-state equilibrium of ligand- and metal-based states (3 n, tt*
<-> 3MLCT). It is clear through ligand manipulation of the transition metal chromophore
that both ligand and metal-based excited states are populated upon photoexcitation, and
the observed emission and transient absorption photophysics are controlled by this
equilibrium.
The effect of oligomer and polymer structure on the observed photophysics.
Altering the repeat unit length or switching from a “linear” to “bent” n-backbone
structure dramatically alters the observed photophysics.
XVII

rc-CONJUGATED POLYMERS
Introduction
The unique optical and electronic properties of ^-conjugated polymers have been
an area of intense research in recent decades.1 These polymers typically have high
fluorescence quantum yields,2 exhibit electrical conductivity,3 and possess non-linear
optical (NLO) properties4'6 that lead to their potential use in organic-based light emitting
diodes (LEDs),7'10 photoconductive or photorefractive devices,11'15 chemical sensors,16'18
and molecular electronic devices.19 20 Two major classes of ^-conjugated polymers are
considered here, polymers with a phenylenevinylene or aryleneethynylene-based subunit
and polymers with a thiophene-based subunit.
Phenylenevinylene- and Aryleneethynylene-Based Polymers
“Rigid rod” polymers with polyphenylenevinylene (PPV) or
polyphenyleneethynylene (PPE) subunits have been popular for their unique material
properties for the past 15 years. Rothberg21 performed extensive photophysical studies on
PPV-based polymers that could serve as a “molecular wire.” The photoexcited electron
(i.e., exciton) can easily travel through the “electron cloud” created along the polymer
backbone by extended ^-conjugation. Typical photophysical properties for PPV as a thin
film include a broad ground state absorption centered at 400 nm and an intense 540 nm
fluorescence.21 Excited-state energies, specifically the triplet excited state, are very
1

2
difficult to measure for PPV and most other ^-conjugated polymers due to the absence of
phosphorescence. However, the energy can be determined via indirect means such as
triplet-triplet energy transfer quenching studies. A report by Monkman and coworkers22
determined the triplet energy with this method for poly(2-methoxy-5-(2’-ethyl-hexoxy)-/>
phenylenevinylene) (MEH-PPV),* calculating a value of 1.27 eV (29.3 kcal mol'1). A
previous estimate of triplet excited-state energies for PPV molecules placed them
between 1.2 and 1.4 eV (27.7 - 32.3 kcal mol'1), which agrees well with this
measurement.
A derivative of PPV, poly(2,5-bis(2’-ethylhexyloxy)-l,4-phenylene-vinylene
(BEH-PPV), has also been very popular in photophysical studies. Additionally, a PPV
polymer has been synthesized that contains a 2,2’-bipyridyl subunit for reasons discussed
later. Both polymers are shown in Figure 1-1.
OR
Figure 1-1: BEH-PPV and 2,2’-bipyridine-containing BEH-PPV
(R - CHCH(C2H5)C6H13 Ref. 24).
See chapter 3 for a more detailed explanation of this technique when it is applied to
oligomers and polymers presented in this text.

3
This BEH-PPV polymer exhibited a 504 nm absorption, a sharp 560 nm emission, and a
broad singlet excited-state absorption that extends into the near-IR. The 2,2’-bipyridine-
containing polymer exhibited absorption and emission maxima at 438 and 510 nm,
respectively. The observed spectral blue-shifts are due to conjugation breaks in the n-
delocalization of the polymer backbone produced by the twisted bipyridine subunits.
This delocalization restriction is an important concept to understand in Tt-conjugated
polymers and will be considered in subsequent chapters. A transient absorption spectrum
of the bipyridine-containing polymer is shown in Figure 1-2. Note the broad excited-state
absorption that extends into the near-IR and the bleach that corresponds to a ground-state
7T,7i* absorption.
Figure 1-2: 2,2’-Bipyridine-containing PPV singlet excited-state difference absorption
spectrum in toluene (Solid line, 417 nm excitation, Ref. 24).
Another polymeric structure consisting of alternating ethynyl and aryl subunits
(polyphenyleneethynylene, PPE) was considered by Davey et al.,2 Le Moigne et al.,5,25
and Swager et al.26 having the structure shown in Figure 1-3.

4
OR
Figure 1-3: Aryleneethynylene-based polymer structure (R = n-octadecyl, Ref. 2).
The additional rigidity in the aryleneethynylene-based polymers compared to the
phenylenevinylene samples allowed for higher emission quantum yields by decreasing the
nonradiative decay rate constant (knr), which could make them more useful in conjugated
polymer applications. Absorption spectra for the polymer shown in Figure 1-3 exhibited
a sharp 452 nm absorption that is assigned as a 7t,7t* transition of the conjugated
backbone. A corresponding sharp emission band with a 482 nm maximum is observed,
as shown in Figure 1-4.
Figure 1-4: PPE absorption (solid line) and emission (dashed line) spectra in chloroform
(Ref. 26).

5
O f* •
Keeping the “molecular wire” idea in mind, Swager and coworkers synthesized
aryleneethynylene-based polymers containing varying amounts of anthracene repeat units
as shown in Figure 1-5.
Figure 1-5: Anthracene-containing aryleneethynylene polymer (Ref. 26).
Photophysical studies of these polymers showed that excitation into absorption bands
associated with the polymer backbone produced emission typically observed for
anthracene and a dramatic reduction in the polymer-based fluorescence. For example, a
polymer with a structure corresponding to x = 0.17 in Figure 1-3 has the absorption and
emission spectra shown in Figure 1-6.
This mixed polymer exhibited the same absorption and emission observed for the
PPE polymer (Figure 1-3), but the presence of new absorption and emission bands at 527
and 549 nm, respectively, result from the anthracene moiety. This observation suggests
that the exciton was efficiently “trapped” by the anthracene subunits. This trapping could
lead to emission or energy transfer to other substituents, which would be utilized in LED
or NLO applications. Therefore, polymers could be synthesized containing unique
subunits (like anthracene in this example) to manipulate (i.e., tune) the excited-state
properties of the polymer. Furthermore, model systems where anthracene moieties were

6
only present at the ends of a PPE 20-mer still exhibited pronounced anthracene emission,
indicating very efficient energy transfer along the polymer backbone (e.g., “exciton
hopping”).26
Figure 1-6: Absorption (solid line) and emission (dashed line) spectra in chloroform of
the polymer in Figure 1-5 with x = 0.17 (Ref. 26).
Zhou and Swager16 continued the defect-trapping idea with aryleneethynylene
polymers containing a cyclophane-based “receptor” as seen in Figure 1-7.
Figure 1-7: Cyclophane-containing aryleneethynylene polymer
(R = CON(C8HI7)2, Ref. 16).

7
The cyclophane polymer exhibited a 427 nm absorbance and intense ( emission. The presence of organic molecules that can associate within the cyclophane
(e.g., methyl viologen) effectively quenched the polymer emission. As little as 60 pM
methyl viologen quenched the polymer fluorescence by an order of magnitude, and 0.1
mM completely quenched the emission. This quenching is due to the formation of
effective “exciton traps” analogous to the anthracene moieties discussed earlier, resulting
in efficient quenching of entire polymer strands with a relatively small amount of the
associating molecule.
Polythiophene-Based Polymers
Another series of ^-conjugated polymers that have received much attention for
their optical properties are polythiophenes. Yamamoto and coworkers first reported the
conductivity of polythiophene in 1980,27 and its ease of oxidation made this polymer very
popular for molecular wire and doping applications. Photophysical data for
polythiophene in solution is difficult to measure, as thiophene oligomers containing six or
more thiophene rings have extremely poor solubilities. For this reason, small molecular
weight oligothiophenes and substituted polythiophenes have been studied that circumvent
this solubility issue.
An exhaustive study by Becker and coworkers28'30 illustrated the effect increased
backbone ^-conjugation has on the observed photophysics. The photophysics of
oligothiophenes ranging in size from one to seven thiophene rings were presented, and
many trends are apparent. The absorption and fluorescence spectra both exhibited red-
shifts with increasing oligomer size (from 232 to 441 nm for absorption; from 362 to 522
nm for emission in dioxane). Emission quantum yields and lifetimes also increased in the

8
larger oligomers, suggesting an increase in the n-delocalization of the oligomer backbone.
Both absorption and emission maxima were found to be inversely related to the oligomer
size, allowing for the estimation of polythiophene values (490 nm absorption; 580 nm
emission). The transient absorption spectra of the oligothiophenes also red-shifted with
increasing oligomer size, with the largest oligomer resembling the PPV spectrum in
Figure 1-2. Absorption and transient absorption spectra of the oligothiophene series are
shown in Figure 1-8.
The absence of phosphorescence in the oligothiophenes eliminated the possibility
of direct determination of their triplet excited-state energies. However, a photoacoustic
calorimetry technique^ was used to indirectly determine the triplet energy, which
decreased from 2.23 eV to 1.60 eV (51.5 - 36.9 kcal mol'1) as the oligomer size was
increased from two to seven thiophene rings.30 The energy was found to be inversely
related to the oligomer size, allowing the polythiophene value to be extrapolated (1.43
eV, 33.0 kcal mol'1). This energy is very similar to the PPV values listed above.
Swager’s use of cyclophane subunits in aryleneethynylene-based polymers (Figure
1-7) was also used with a polythiophene backbone as shown in Figure 1-9. The
cyclophane-containing polythiophene exhibited a 520 nm absorption and 624 nm
emission that is considerably weaker than the PPE polymer (<|)em = 0.066). This emission
intensity decrease is due to the greater flexibility of the polythiophene backbone, which
provides an alternative non-radiative mechanism for excited-state deactivation through
molecular motion. The polymer fluorescence was also quenched by organic molecules
’’’ See chapter 2 for a more detailed explanation of this technique and chapters 3 and 5 for
its application to determine triplet excited-state energies and yields.

9
(e.g., methyl viologen) as before, indicating efficient exciton trapping by the cyclophane
subunits. The quenching rate is smaller for this polymer than the PPE polymer, however,
due to the weaker polythiophene emission intensity.
Figure 1-8: Absorption (in dioxane) and triplet-triplet absorption difference spectra (in
benzene, 347 nm excitation) of an oligo(thiophene) series. The a number indicates the
number of thiophene rings in the oligomer. (Ref. 28-29)

10
Figure 1-9: Cyclophane-containing polythiophene polymer (R = C10H21, Ref. 16).
While polythiophenes have many interesting properties, their solubilities are very
poor. Furthermore, they can be oxidized by atmospheric oxygen, limiting their
processibility and stability in materials applications.31 Elsenbaumer and coworkers32
synthesized an alkylated derivative of polythiophene in 1986 that was soluble and
considerably more stable. Four different coupling structures are possible in these
alkylated polymers, which are illustrated in Figure 1-10.
Head-to-Tail-Head-to-Tail Tail-to-Tail-Head-to-Tail
Coupling (HT-HT) Coupling (TT-HT)
Head-to-Tail-Head-to-Head Tail-to-Tail-Head-to-Head
Coupling (HT-HH) Coupling (TT-HH)
Figure 1-10: Poly(3-alkylthiophene) repeat structures (Ref. 33).

11
It was found that the increased structural homogeneity improved the conductivity
and optical properties of the polymer by increasing the effective conjugation lengths
within the polymer strands.33 34 Random connection patterns prevented the polymer from
achieving the coplanarity necessary for extended ^-conjugation via steric interactions. In
recent years, synthetic techniques have been refined to produce highly regiospecific
polythiophenes for materials-based applications. ’ Absorption spectra of HT-HT
poly(3-alkylthiophenes) in chloroform solution exhibit a broad absorption band centered
at 436 nm. Varying the alkyl chain lengths from hexyl to dodecyl did not change the
solution absorption spectra but induced a red-shift of the solid-state absorption spectrum
by 15 nm from the shortest to longest alkyl chain. Note that the absorption maximum
of a TT-HH poly(3-decylthiophene) is 312 nm in chloroform,36 significantly blue-shifted
from the HT-HT polymer and confirming the need for regiospecific polythiophenes to
achieve the maximum extended conjugation. The polymer extended ^-conjugation
exerted a similar effect on 3-alkylthiophenes as seen earlier on the oligothiophenes, as the
major absorption band of a series of oligo(3-octylthiophene)s in chloroform red-shifts
from 302 to 405 nm with increased oligomer size from two to six thiophene rings. This
trend indicates a consistent lowering of the LUMO energy.37
Unlike the PPV and PPE-type polymers, phosphorescence has been observed at
low temperature (18 K) for poly(3-hexylthiophene) by Xu and Holdcroft.38,39 A sharp
826 nm phosphorescence was observed, leading to a calculated triplet excited-state
energy of 1.50 eV (34.6 kcal mol'1). This value is higher than the MEH-PPV and
polythiophene triplet energies (1.26 eV), which is surprising since the alkylated thiophene
is a more planar polymer, which should increase the delocalization and lower the energy.

12
This observation could be due to the regiospecificity of the phosphorescence sample, but
Xu and Holdcroft reported that various regiochemistries were investigated with similar
spectral results. Also, the MEH-PPV triplet energy was determined by qualitative
quenching studies,Í which could result in a large error.
MLCT-Incorporated ^-Conjugated Polymers
The initial photophysical work on n-conjugated polymers, coupled with the desire
to more easily control their excited-state characteristics, led to the idea of introducing
inorganic MLCT (metal-to-ligand charge transfer) chromophores into the polymer
backbone. These chromophores have excited states that can easily be tuned by ligand
substitution, potentially allowing a greater capacity to tune the polymer excited
state(s).40'42 Following the initial idea, the synthesis and photophysical properties of
these metal-organic ^-conjugated polymers have rapidly grown in interest.43'48
Phenylenevinylene- and Aryleneethynylene-Based Polymers
Yamamoto and coworkers first suggested the introduction of MLCT
chromophores into ^-conjugated polymers during his studies on poly-2,2’-bipyridine.49'52
The bipyridine repeat unit allows easy ligation of ruthenium, nickel, copper, and iron
chromophores, as shown with the -Ru"(bpy)22+ chromophore (bpy = 2,2’-bipyridine) in
Figure 1-11.
Í In the study, when a triplet acceptor (tetracene, ET = 1.27 eV) did not quench the triplet-
based transient absorption of MEH-PPV, the polymer triplet energy was “estimated” to be
that value.22

13
Figure 1-11: Poly-2,2’-bipyridine ruthenium-containing polymer (Ref. 50).
The resulting metal-containing polymers exhibited electrochemical data largely
representative of the MLCT chromophores, including Ru" —> Ru111 oxidation and
2,2’-bipyridine reduction. Since these polymers were synthesized for their photocatalytic
and photoelectrochemical properties, little photophysical work other than an absorption
spectrum in methanol was published. This absorption spectrum contained bands
originating from both the polymer 7i,7i* and ruthenium MLCT transitions at 373 and 450
nm, respectively. A copper(II)-containing polymer was also synthesized where a single
copper atom had the capability to ligate two adjacent polymer strands. Absorption
spectra of the copper-containing polymer exhibited a 20 nm red-shift in both the polymer-
based 71-71* absorptions and the metal-based MLCT transition when compared to model
monomeric systems, indicating lowered LUMO energy levels due to increased
delocalization.
An alternative method for introducing transition metal chromophores into
7r-conjugated polymers involves direct metal center substitution into the polymer chain.

14
Wittmann and coworkers'3 54 synthesized aryleneethynylene-based polymers containing
Pd[P(C4H9)3]2 or Pt[P(C4H9)3]2 subunits as shown in Figure 1-12.
Figure 1-12: Aryleneethylylene-based polymers containing platinum subunits
(M = Pd or Pt, Ref. 53).
This synthetic approach produces very consistent polymer products and interesting
photophysical results. An intense 380 nm singlet and weaker 510 nm triplet ground state
absorption were observed in solution studies of this polymer, which is red-shifted from
the model monomer spectrum (345 nm). This red-shift reflects a clear increase in
delocalization across adjacent n orbitals in the polymer backbone. A broad 520 nm
luminescence was also observed from the polymer sample. However, due to their
position within the polymer backbone these metal chromophores lack the “tunability”
options available in other MLCT-based chromophores that are attached to the polymer
backbone like the ruthenium chromophore in Figure 1-11.
Work pioneered by Yu and coworkers produced a significant advance in MLCT-
containing n-conjugated polymers by introducing the well-known and characterized
Ru(bpy)32+ and Os(bpy)32+ chromophores into a PPV-type polymer shown above (Figure
1-1) through an ingenious Heck coupling reaction.43,44’55 The polymer structure is shown
in Figure 1-13.

15
Figure 1-13: Ru(bpy)32+-containing PPV polymer (R = n-heptyl, Ref. 43).
These polymers exhibit interesting photoconductivity, photorefractivity, and NLO
properties. The all-organic polymer (x = 0, y = 1 in Figure 1-13) exhibited an intense
7i,n* transition absorption at 470 nm, while the all-metal polymer (x = 1, y = 0) had a 550
nm “MLCT”§ absorption. A mixed polymer (x = 0.1, y = 0.9) absorption spectrum
exhibited a superposition of the two bands. Extensive work was performed on the
material properties of these polymers listed above, but the studies did not extensively
probe the basic photophysical properties of the polymer excited state(s).
Further work was performed on these polymers by Wasielewski and
coworkers,24’56 including work where the polymer backbone was used as an ion sensor.18
The complexed metal ion induced a conformational change in the 2,2’-bipyridine polymer
subunit, which is twisted and serves as a break in the polymer 7t-conjugation as discussed
earlier. The bipyridine was coplanar after complexation, resulting in a conjugation
increase within the polymer as seen in Figure 1-14. This conjugation increase led to
differing photophysical properties that signal the presence of the analyte ion (e.g., red-
§ The molar absorptivity for this transition (ca. 90 x 103 M'1 cm'1) is rather high for an
MLCT transition. However, the high concentration of ruthenium and the extended
delocalization of the polymer backbone might contribute to its high value.

16
shifted absorption and emission bands) due to a lowering of the LUMO. For example,
when nickel(II), zinc(II), or palladium(II) ions were titrated into a solution containing the
2,2’-bipyridine-containing PPV, the polymer 7t,7t* 450 nm absorbance red-shifted
between 50 - 100 nm depending on the metal ion. The ionochromic effect exhibited in
these polymers proved to be an excellent ion-sensing device.56
Figure 1-14: Conformation change upon metal complexation (R = decyl, Ref. 18).
In the wake of the PPV research, other ^-conjugated polymers containing
inorganic MLCT chromophores have also been investigated. Rasmussen et al.57 made
ruthenium-containing polymers with a poly-diazabutadiene / 2,2’-bipyridine backbone as
seen in Figure 1-15. An absorption spectrum of the polymer showed an intriguing blue-
shift from a dimer model oligomer (from 480 to 465 nm in DMF). However, the polymer
band was significantly broader, suggesting a myriad of accessible electronic transitions.
The observed emission spectrum remained the same (sharp 666 nm band) for the two
systems, but the polymer quantum yield was one-fourth the dimer value. This trend

17
suggested that increased nonradiative decay or decreased intersystem crossing to the
emissive 3MLCT might result from the extended ^-conjugation.
Figure 1-15: Ruthenium-containing diazabutadiene polymer (Ref. 57).
co
More recently, Wong and Chan synthesized PPV-type polymers that have
ruthenium chromophores attached via an alkoxy chain, as shown in Figure 1-16. This
polymer configuration provides even greater ligand substitutional flexibility but removes
the MLCT chromophore from direct interaction with the polymer ^-conjugation, thus
limiting its effects on the polymer excited state(s). The purpose of these polymers was to
form metal-organic LEDs, with the chromophore not serving as a “tuning control” for the
polymer excited state(s) but as a dopant to produce the electrogenerated luminescence. A
(x = 0.1, y = 0.9) polymer exhibited a 444 nm absorption and 606 nm emission in DMF
solution, which is very similar to monomeric Ru(bpy)32+ photophysics. These data
indicate little electronic interaction between the polymer and MLCT chromophore.
LEDs fabricated from these polymers exhibited good current-voltage properties
and serve as an excellent starting point for “tunable” LEDs by varying the ruthenium

18
ligands. Clearly, the topic of MLCT-incorporated ^-conjugated polymers is of great
recent interest, and many other polymer structures are available for exploration.
Figure 1-16: PPV-type polymer with tethered ruthenium chromophores
(Ru = Ru(bpy)32+, Ref. 58).
Polythiophene-Based Polymers
Introducing MLCT chromophores into thiophene-based polymers has also been
studied, but to a lesser degree than the PPV and PPE-based polymers. Zhu and
Swager59,60 synthesized a Ru(bpy)22+-containing polythiophene via ligation to a 2,2’-
bipyridine polymer subunit, as seen in Figure 1-17.
Figure 1-17: Ru(bpy)32+-substituted polythiophene (Ref. 59).
The monomer repeat unit of the unmetallated polymer exhibited a sharp 400 nm
absorption in methylene chloride, which is blue-shifted from the estimated native

19
polythiophene value (490 nm) for the same reasons discussed above for the
2,2’-bipyridine-containing PPE polymers. Further work by Zhu and Swager17’61 focused
upon thiophene polymers containing metallorotaxane centers with zinc or copper ions, as
shown in Figure 1-18.
Figure 1-18: Metallorotaxane-thiophene polymers (M = Zn2+ and Cu2+, Ref. 17).
These rotaxanes exhibited marked improvement in stability over the bipyridine-
containing polythiophenes (Figure 1-17) and improved conductivity over native
polythiophene. Detailed photophysics, however, were not presented in this study.
Reddinger and Reynolds synthesized another novel thiophene-based polymer
containing MLCT chromophores.62'63 In these polymers, a nickel or copper chromophore
was complexed to a SALOTH ligand that was incorporated into the thiophene backbone
as shown in Figure 1-19. This polymer showed excellent conductivity properties, but
again its photophysics were not the major focus of the reported research.

Figure 1-19: SALOTH thiophene polymer (M = Ni" and Cu11. Ref. 62).
Previous Group Work
Based on the previous work described above, it was obvious to our group that
while many different inorganic MLCT chromophore-containing rt-conjugated polymers
were being synthesized and applied in various materials applications, little detailed
photophysical work had been performed to explore their excited state energies and
dynamics. To that end, a project was initiated to synthesize polymers combining some of
the ideas explored by previous groups. The work by Yamamoto and coworkers49'"2 and
Yu and coworkers43’44’5" incorporating MLCT chromophores through a 2,2’-bipyridine
subunit in the polymer backbone was desirable since it afforded maximum tunability
when selecting MLCT chromophores such as ruthenium, rhenium, and osmium
complexes. Also, the increased rigidity of the aryleneethynylene-type polymers was more
favorable than PPV-type structures. This rigidity would provide larger transition dipoles
and hopefully more pronounced photophysical behavior. Therefore, a polymer structure
combining both of these elements was devised and implemented.
A series of ^-conjugated aryleneethynylene polymers with varying incorporated
amounts of the well-characterized -(bpy)Re‘(CO)3Cl chromophore41 were synthesized via

21
Sonogashira coupling64 and their photophysical properties investigated in our lab.45,46,65
The polymer structures, along with typical polymer weights obtained from GPC
experiments, are shown in Figure 1-20.
P1 : Mw = 37 kg mole'1, Mn = 14 kg mole'1, PDI = 2.7
Re (CO)3CI
P2 : x = 0.10, y = 0.90; Mw = 21 kg mole'1, Mn = 8.8 kg mole'1, PDI = 2.3
P3 : x = 0.25, y = 0.75; Mw = 16 kg mole'1, Mn = 7.9 kg mole'1, PDI = 2.1
P4 : x = 0.33, y = 0.67; Mw = 26 kg mole'1, Mn = 11.3 kg mole’1, PDI = 2.3
P5 : x = 0.50, y = 0.50; Mw = 16 kg mole'1, Mn = 7.8 kg mole'1, PDI = 2.0
R = n-C18H37
Figure 1-20: Aryleneethynylene polymers containing (bpy)Re'(CO)3Cl (Ref. 46).
Metal-organic polymers P2 - P5 exhibited many unique photophysical properties,
including a red-shifted absorption band and unique long-wavelength luminescence when
compared to the “all organic” polymer PI. These observations were believed to arise
from a dn (Re) —» 7t* (bpy-polymer) MLCT transition as seen in the PPV-based polymers
presented above (Figure 1-13), which is typically observed for transition metal MLCT
chromophores.41 Studies on model monomeric compounds that duplicated the repeat
structure of the polymers initially supported this theory. However, certain photophysical

22
results were puzzling. For instance, the introduction of the rhenium MLCT chromophore
into the polymer backbone decreased the polymer fluorescence quantum yield and
lifetime, which would be expected due to the chromophore acting as an “exciton trap” as
described above. However, polymer-based fluorescence was not completely quenched in
even the P5 polymer, which was unexpected. Polymers P2, P3, and P5 were synthesized
by a random copolymerization process, resulting in an inability to accurately characterize
the polymer segment sequencing. Specifically, it was unclear whether the transition
metal segments were homogeneously distributed throughout the polymer or segregated
into “all organic” and “all metal” sections within the synthesized polymer. The
inefficient fluorescence quenching suggested that a heterogeneous polymer was being
produced by this procedure, allowing the organic polymer segments to behave as if the
metal chromophore was not present. Further synthetic developments allowed for the
synthesis of polymer P4, which has a known (organic, organic, metal) repeat structure.
Nonetheless, it was evident that further work based on model systems containing this
repeat structure was necessary to better interpret the polymer photophysical observations.
Scope of This Work
To further understand the photophysics observed for PI - P5, a series of
well-defined oligomers containing various lengths of the original polymer repeat structure
were synthesized using a novel iterative synthetic scheme based around palladium-
mediated coupling reactions. The detailed photophysical results of both free oligomers
and oligomers bound to the Re^CO^Cl chromophore are presented herein. Next, the
repeat units and geometries of the oligomers were varied to see how these changes affect

23
the observed photophysics. Particular attention is paid to the oligomer conjugation length
influence and/or the possible formation of aggregates on the observed photophysical
properties. Many spectroscopic techniques, including absorption, emission, transient
absorption, electroabsorption spectroscopy, and transient EPR were utilized to probe the
molecular excited state(s). Also, in a collaborative project with Dr. Stephan Guillerez
and Lise Trouillet at CEA-Grenoble, the photophysical properties of poly(3-
alkylthiophenes) with the capacity to complex MLCT chromophores through an
integrated 2,2’-bipyridine subunit were studied in order to investigate the influence of the
transition metal on their excited-state properties. The polymers are similar in structure to
the Swager polymer shown in Figure 1-17 but with the added alkylation stability. Before
these photophysics are discussed, however, a class of techniques that utilize the evolution
of heat after photoexcitation to determine excited-state energetics is presented. This
technique, photothermal chemistry, has received little attention in the study of inorganic
complexes but is successfully utilized in the photophysical study of our PPE-type
oligomers and polymers.

PHOTOTHERMAL CHEMISTRY
Photothermal chemistry involves the study of electronic transitions through the
radiation of heat instead of light. The majority of photothermal chemistry studies in the
literature rely on one of two techniques: Thermal lensing spectroscopy and photoacoustic
spectroscopy. Thermal lensing spectroscopy involves a change in the sample refractive
index due to released heat, resulting in the diffraction of a probe laser beam.66,67
Photoacoustic spectroscopy uses a piezoelectric transducer to analyze pressure waves in a
sample caused by the emission of heat.68,69 The main advantage of studying excited states
with photothermal studies is the lack of dependency upon the emission of light, which
greatly increases the number of molecules that are amiable for study.
Both techniques have distinct advantages and disadvantages. Photoacoustic
spectroscopy has a shorter (nanosecond to microsecond) observation time window than
thermal lensing spectroscopy and requires external calibration, resulting in additional
sample runs and increased experimental time.70 Time-resolved thermal lensing (TRTL)
spectroscopy, however, has a long (tens of microseconds) observation time window and
requires no external calibration.71 Furthermore, photoacoustic spectroscopy does not
need to correct for probe beam absorption and can more readily study complex, multiple-
process excited-state behavior. Both techniques will be addressed in turn, followed by
their application to the study of inorganic and organic photophysics.
24

25
Theory
Time-Resolved Thermal Lensing
The premise of TRTL is very simple. A sample is irradiated with a pump laser,
producing an excited electronic state. A second probe laser is then directed through the
photoexcited sample. These two beams are commonly in a longitudinal (colinear)
geometry, but they can also be applied in a transverse (perpendicular) configuration. Any
heat evolved by the sample excited state decay(s) will cause a change in the sample
refractive index and subsequent probe beam refraction (i.e., the formation of a “thermal
lens”). A decrease in the probe beam center intensity can therefore be related to heat
released by the sample.67 The pump beam is removed from the optical path by a filter or
dispersing prism, and the probe beam center is usually isolated by a pinhole or knife edge
for intensity measurement. Figure 2-1 shows a basic TRTL apparatus.
».y,z splitter *,%i
plotform plotform
Figure 2-1: Basic TRTL longitudinal apparatus (Ref. 70).

26
The thermal lens theory
The thermal lens effect (also known as "thermal blooming") was first reported by
Gordon and coworkers over 30 years ago. It was initially considered a hindrance to
other laser spectroscopic methods, but Gordon determined that the degree of laser beam
refraction was related to the sample solution refractive index. Since the refractive index
of a liquid changes with temperature, the induced refraction can be related to heat given
off by the photoexcited sample. The thermal lens does not form immediately upon the
release of heat and slowly decays based on the thermal conductivity of the sample, so
time-resolved experiments can also be performed.66
The thermal lens focal length in a "steady state" equilibrium, f(oo), is given in
(2-1). This value can be used in (2-2) to calculate the thermal lens focal length at time t,
f(t), during a TRTL experiment.
(2-1)
f(t)=f(»)il + ^£ll (2-
w v \ 8kT J
In (2-1) and (2-2), k is the sample thermal conductivity (W cm'1 K'1), co is the Gaussian
probe laser beam spot size (cm2), P is the probe beam power (W), A is the sample
absorbance, ^ /gjJ *s the refraction index variation with temperature, p is the sample
density (g cm'3) and Cp is the specific heat of the sample (J g'1 K'1). These equations do
not take into account any sample luminescence, and all excitation energy is assumed to be

27
released as heat. Appropriate corrections can be used if any appreciable luminescence
occurs concurrent with the emission of heat.66
If a TEMoo Gaussian laser beam is used for the probe, equations can describe the
beam diffraction based upon the thermal lens effect. The variables used in ensuing
equations are visually defined in Figure 2-2. The relative probe beam area change at the
pinhole, Aco2, is defined in (2-3),73 while the beam center intensity change at the pinhole,
Albc, is defined by (2-4).66
Pinhole
Figure 2-2: Thermal lens Gaussian probe beam divergence (Ref. 66).
Aco2
-2.303P
{%}
A j
2(Zl)Zt )
co2
Xk
K.
y
Ui+(zi)!J
(2-3)

28
--2-30w=2,03EA
I
be
Xk
(2-4)
In (2-3) and (2-4), X is the probe laser wavelength and Zc is the confocal distance
J. E is a simplified instrumental value of the various constants in (2-3), since
they should not change during the experiment. Therefore, a variation of sample
absorbance should produce a linear relation and allow the sample refraction change with
temperature to be determined. Both (2-3) and (2-4) are considered the fundamental
TRTL theory equations, but they are rarely used in everyday experimental practice.
Another treatment of TRTL theory74 discusses the relationship of the sample
refractive index change and the commonly-used TRTL signal, S(t), which is defined in
(2-5). The proposed equation for this relationship, assuming longitudinal geometry of the
pump and probe beams, is given in (2-6).
Vo-V(t)
s(t)=
(2-5)
SL(t) =
8aE0ljZ,
rcpCr
dr/ '
/dT
a +8Dt
2 4(x~vxt)
a2 +8Dt
2
exp
-2(x-vxt)
a2 + 8Dt
2 A
(2-6)
In (2-5), Vo is the intensity of the probe beam center before pump beam excitation and
V(t) is its intensity at time t after pump excitation. Therefore, S(t) can vary between 0 (no
beam divergence) and 1 (“complete” theoretical beam divergence). In (2-6), the sample is
assumed to be analyzed perpendicular to the sample flow which has a velocity of vx, a is
the absorption coefficient, Eo is the pump beam energy, 1¡ is the pump/probe beam
interaction length within the sample, a is the probe beam Gaussian radius, and D is the

29
...91 ...
sample thermal diffusivity (m s'). An equation similar to (2-6) can also be derived for
the transverse (perpendicular) orientation of the pump and probe beams. Both (2-4)66 and
(2-6)74 show the relationship between the sample refractive index change (e.g., evolution
of heat) and the degree of probe beam diffraction. Although these equations are complex,
it is not necessary to use such quantitative measurements of thermal lensing to
calorimetrically determine excited state energies and excited state process quantum
yields.
A simplified calculation method
The calculation scheme presented here for TRTL studies was first used by
Braslavsky and coworkers in a study of singlet oxygen quantum yields of various organic
sensitizers.7:1 If the analyte under study involves a single, long-lived triplet state
following intersystem crossing from an emissive singlet state (many organic
photochemical systems of interest fall into this category), then (2-7) can be applied to
determine the intersystem crossing quantum yield (Oise).
^Slow _ ^ISC^T
U Total Eex-0flEs
In (2-7), Et is the triplet excited state energy, Eex is the pump laser energy, On is the
fluorescence quantum yield, and Es is the singlet excited state energy. If either Oise or ET
is known from other photophysical measurements, TRTL can be used to determine the
unknown parameter. Usiow and Uiotai values are obtained directly from the TRTL
spectrum. A sample TRTL response of phthalazine, which qualifies for the use of (2-7),
measured in benzene by Terazima and Azumi71 illustrates Usiow and Uiotai and is shown in

30
Figure 2-3. TRTL intensity (S(t) from (2-5)) is plotted versus time after pump beam
excitation.
Figure 2-3: TRTL spectrum of phthalazine in benzene (Ref. 71).
In Figure 2-3, Uiotai represents the entire heat given off by the sample after pump
laser excitation (occurring at t = 0 ps), while Usiow represents the heat gradually given off
by the nonradiative decay of the triplet excited state to the singlet ground state. The fast
heat (Uiotai - Usiow) immediately given off at time zero represents fast processes (e.g.,
fluorescence and intersystem crossing) with lifetimes faster than the acoustic transit time
75 R
(xa) of the sample (ta = —; R = radius of probe beam, ua = velocity of sound in the
«a
sample medium), which was around 50 ns for Terazima and Azumi.71 A third

31
component, a gradual decay of the TRTL signal on the order of milliseconds resulting
from thermal conductivity within the sample, is not shown in Figure 2-3.
The true beauty of this method is that no calorimetric standards are required to
measure ®isc (or Ex), so long as the other variables in (2-7) are determined by other
spectroscopic techniques. A plot of log[Ux0tai - S(t)] versus time can yield a linear plot
from which the triplet lifetime can be calculated. The only specific requirement for this
calculation method is that the triplet excited state lifetime must be longer than about 4ia.
(200 ns in the Terazima and Azumi example)71 but shorter than the thermal conductivity
decay time of the sample (usually a few milliseconds). If the excited state lifetime is
outside these boundaries, Usiow cannot be distinguished from UFast in the TRTL spectrum.
It is important to note that (2-7) presumes that fluorescence is the only alternative
zo
decay process to the release of heat. If phosphorescence (e.g., emission from the triplet
excited state) is observed instead of fluorescence, (2-7) must be adapted to allow for this
new excited-state deactivation pathway, as shown in (2-8).
Usiow _ ET(l-em) g
U Total Eex -ET+ET(l-®em)
In (2-8), ®em is the triplet phosphorescence quantum yield. The intersystem quantum
yield is assumed to be unity, which is valid for most inorganic chromophores due to spin-
orbit coupling induced by the presence of heavy atoms.76 Equations like (2-8) can easily
be derived for other photochemical systems with multiple excited state processes.
However, for complex systems photoacoustic spectroscopy is likely to be more
informative.
See Figure 2-4 for a TRTL spectrum with this component.

32
Limitations and instrumental considerations
One problem experienced in TRTL spectroscopy results from the presence of
singlet oxygen. If singlet oxygen is produced by the excited state quenching process, its
decay is readily observed in the thermal lens response (and possibly falsely interpreted as
an excited-state decay of the analyte).77 While this may be a hindrance in many
experiments, TRTL can provide an easy singlet oxygen detection method if it is an
expected product in a photochemical process. However, if this decay is not desired
rigorous degassing of all samples should be performed prior to experimentation to
eliminate the possibility of its production.
The main culprit by far in TRTL that leads to errant signals is the absorption of
the probe beam by the sample. The excited state of most inorganic chromophores
produced by photoexcitation readily absorbs at visible wavelengths typically used for the
probe laser, which results in an erroneously high TL signal.68 Chartier and coworkers
have also observed abnormal TRTL signals with erythrosine that are attributed to an
excited-state triplet-triplet absorption at the probe beam wavelength.78 This errant signal
was characterized by a rapidly decaying component in the TL signal that was readily
eliminated with the addition of oxygen to quench the excited state absorption. These
abnormal TL signals are obvious in the spectra in Figure 2-4. The excited state
absorption error can be reduced with an appropriate apparatus design, as described below.
The majority of all TRTL experimentation is performed with an apparatus similar
to that in Figure 2-1. An extensive study by Berthoud and coworkers analyzed the
optimal beam geometries for the pump and probe laser beams.79 They determined that for
maximum TRTL sensitivity and resolution the pump beam should be focused in the

33
sample cell, while the probe beam should be focused about 10 cm in front of the cell.
Since the thermal lens spreads the probe beam, if its focus is before the sample the beam
will already be diverging through the sample cell. Therefore, the beam divergence will
further increase after passing through the sample thermal lens, increasing the sensitivity
of the technique. If the probe beam is focused after the cell, the thermal lensing signal
will be inverted relative to the typical TRTL spectrum (i.e., the probe beam center
intensity increases as heat is given off). If the probe beam focus is after the sample the
beam will be diverging after the thermal lens before it reaches the beam waist, resulting
in a smaller probe beam after the beam focus.74 With these optimal conditions, it was
determined that the detection limit for TRTL could be as much as two to three orders of
magnitude lower than those determined for absorption spectrophotometry (* 1 x 1 O'8 M
for a strongly absorbing species).79,80
Figure 2-4: Time-resolved pulsed thermal lens signal obtained for 10'5 M erythosine in
water (Ref. 78). (a) air saturated; (b) oxygen-saturated; (c) nitrogen-saturated.

34
Several other instrumental concerns must be considered. The pinhole radius must
be at most 1/10 the radius of the probe beam to ensure accurate measurement of only the
beam center intensity. This pinhole is placed about 2.5 - 3 m from the sample to allow
maximum probe beam divergence and, consequently, instrumental sensitivity. Also,
experimentation81 concluded that the probe beam radius should be approximately four
times the size of the pump beam radius for optimal response. The laser beam diameter
manipulation cannot simply be done with apertures, as Fresnel diffraction rings would be
created which would severely distort the intensity measurement. Instead, a laser
telescope should be used to properly size the pump and probe beams.81 The sample is
commonly in a flow cell to ensure a constant supply of ground state analyte molecules
and reduce sample degradation from extended periods of photoexcitation.67 The majority
of the referenced studies use the longitudinal pump and probe beam geometry with both
beams overlapping each other in a collinear and concentric manner within the sample
cell.
Cambrón and Harris devised a more complicated TRTL apparatus to help alleviate
the concern of any possible probe beam absorption.73 Their apparatus is illustrated in
Figure 2-5. The key feature of their design is the use of a second PMT detector (after L5
in Figure 2-5) that measures the intensity of the entire probe beam after it passes through
the sample. This “time-resolved” reference signal corrects for any laser fluctuations and,
more importantly, sample excited-state absorbance of the probe beam after pump
excitation. This design feature will be implemented in our study.

35
L2 L4 B A g P
Figure 2-5: TRTL apparatus with probe beam absorption compensation (Ref. 73).
Photoacoustic/Laser-Induced Optoacoustic Spectroscopy
Instead of monitoring heat evolution through a refractive index change,
photoacoustic spectroscopy "listens" for the shock waves that travel through the sample
medium as heat is released. The pressure waves are detected with a piezoelectric
transducer that is placed in contact with the sample cuvette, as seen in Figure 2-6.
Heavily damped transducers are used to keep the relaxation time short and allow for
better temporal resolution while minimizing the influence of shock wave reflections
within the sample cell on the observed signal. The transducer response versus time
illustrating the shock waves produced by heat emission is shown in Figure 2-7. The
initial signal spike in the figure indicated by the arrow is the only usable data in this plot,
as all subsequent responses are reflections of the shock waves off the sides and bottom of
the sample cuvette.
Initially, it was believed that photoacoustic techniques would not be as practical as
TRTL for our research purposes, as it has a limited time window and required the

36
purchase of piezoelectric transducers and a preamplifier. However, photoacoustic
spectroscopy has the marked advantage over TRTL measurements in that no
implementations are needed to correct for any sample excited-state absorption of the
sample under investigation. Photoacoustic spectroscopy measures pressure waves instead
of light, so transient light absorption is not a concern.
Figure 2-6: Basic photoacoustic experimental setup (Ref. 69).

37
Figure 2-7: Typical photoacoustic response (Ref. 69).
Early photoacoustic techniques
Early photoacoustic experiments sought to determine the conversion efficiency of
photoexcitation energy to heat (a) as determined in (2-9).
hue =S(OiEi)+aEex (2-9)
In (2-9), all relaxation processes of a particular excited-state system are included in the
summation, where $¡ is the excited state process quantum yield and E¡ is the retained
energy of that process. A conversion efficiency of 1 indicates all the excitation energy is
released as heat only during the experiment timescale.t A specific quantum yield or
process energy can be determined from (2-9) (if all other parameters are known by other
methods) by calculating a in (2-10).
U = KaIL(l-10*) (2.,0)
^ Common examples of these a = 1 systems are benzophenone, ferrocene and crystal
violet.83

38
In (2-10), U is the initial photoacoustic signal spike intensity (e.g., the "heat" given off by
the sample), II is the laser power, and K is an experimental constant that is determined
from a calorimetric standard with a known a value.
If for an unknown system is plotted versus 1 - 10'A, a line is obtained with a
slope equal to Ka. If an additional plot is constructed with data obtained from a
calorimetric standard and compared to the plot of the unknown system, a for the
unknown can be calculated as illustrated in Figure 2-8. The conversion efficiency can
then be applied in (2-9) to determine the unknown quantum yield or excited state energy
for the analyte molecule.
While this calculation technique is straightforward, it fails to provide any time-
resolved information for multiple excited-state processes, and the use of calibration
standards can greatly complicate the procedure and increase the chances for error.
Therefore, our attentions were turned to a modified photoacoustic technique, Laser-
Induced Optoacoustic Spectroscopy (LIOAS).
Laser-induced optoacoustic spectroscopy
LIOAS observes in a time-resolved manner the pressure waves produced by either
heat released from a photoexcited sample or structural volume changes following
excitation. The evolution of heat is central to our interest in the technique, and
corrections for volume changes will be discussed later. The evolution of the transducer
response to pressure waves with time (V(t)) is defined in (2-11).84

39
Figure 2-8: Photoacoustic calibration plots. Circles are benzophenone (reference) data
points, while crosses are pyridazine (unknown) data points (Ref. 83).
u
v(t)=
h0A U
2 (1
u + —
Wj
\2
exp
f-0
-exp
f_t)
cos(ut)—— sin(ut)
\ X J
lT0 J
L ut'
(2-11)
h A
In (2-11), —5— is an instrumental constant, u is the transducer characteristic oscillation
47rr0
frequency, To is the transducer relaxation time, x is the excited-state process lifetime, and
— = . Equation (2-11) was used to model simulated transducer responses with
XXX,
various excited-state lifetimes, and the responses are shown in Figure 2-9.

40
Figure 2-9: Simulated transducer responses based on (2-11) with varying x values as
indicated, where u = 1 x 106 Hz and To = 1 ms (Ref. 84).
It can clearly be seen that any transducer response falls into one of three
categories. Exceedingly short timescale processes (x < 1 ns, the fast lifetime response
region) all produced the same waveform. Medium lifetime processes (x = several ns to a
few ps) resulted in a response phase shift and amplitude decrease, and long lifetime
processes (x = several ps and greater) became indistinguishable with the baseline. Also,
the delineation between lifetime categories is governed by both the characteristic
frequency of the transducer and the previously defined acoustic transit time of the sample
Of
(xa), which represents the theoretical lower limit of detectable excited-state lifetimes.
In order to extract information from the transducer response signal, deconvolution
using an iterative nonlinear least squares algorithm82 is necessary. This technique
requires three separate data sets for one measurement: 1) A baseline signal; 2) A fast
lifetime reference signal (i.e., a sample which releases all excitation energy as heat in a

41
single fast lifetime process); and 3) A sample signal. To minimize the use of correction
factors in the data analysis, the sample and reference signals are in the same solvent and
with matched excitation absorbances. These signals are normalized by subtracting the
baseline signal and dividing by both an absorbance factor (1 - 10'A) and the average
excitation laser pulse energy. Only the first few oscillations are selected for analysis
since subsequent oscillations are acoustic reflections from the sample cell walls. In the
deconvolution process, fast lifetime excited-state processes will be grouped together into
one component with a meaningless lifetime fit but the correct amplitude (i.e., the total
heat fraction released by the sample from all fast lifetime processes). Medium lifetime
processes produce meaningful amplitudes and lifetimes. Long lifetime processes should
not be detected by the transducer. While LIOAS is used mostly in aqueous media
biological applications, the technique can be applied to organic and inorganic systems in
nonaqueous solutions to distinguish between multiple excited-state processes.
Accounting for solution volume changes
As noted earlier, the main possibility for LIOAS measurement error involves
transducer response correction for any sample structural volume changes (AVr). These
volume changes can be due to either photoexcited molecule structural changes or solvent
molecules ordering around the excited analyte. If we assume that each of the components
obtained from the deconvolution process discussed previously contains contributions
from both thermal and volumetric changes, (2-12) can be derived.86
Eex V a J
(2-12)

42
In (2-12), cpj is the deconvolution amplitude for excited state process i, cp is the
solvent heat capacity, p is the solvent density, and a is the solvent thermal expansion
coefficient^ The first term in (2-12) is the contribution due to emitted heat, while the
second term is due to structural volume changes. These terms can be separated on the
basis of altering the solvent thermal expansivity parameters. The majority of LIOAS
studies focusing on reaction volume changes85,86 were done in aqueous solution, which
allows for easy manipulation of these parameters due to the significant temperature
dependence of a in water. The same parameter manipulation can be achieved in
nonaqueous environments by making several LIOAS measurements in a series of similar
solvents. This strategy was used in studies with a series of n-alkane solvents.87,88 Of
course, the assumption must be made that the analyte photochemistry is similar in each of
the solvents in the series, so care must be taken when selecting the series. If a plot is
c p
made of Eemcp¡ versus ——, a linear relation is expected with a slope of 0,AVr,i (the
a
volumetric component of the signal) and an intercept of 0,E, (the thermal component of
the signal).
It is important to note that Hung and Grabowski88 suggested the assumption that
all observed LIOAS signals are thermal in nature leads to only “small calculation errors”
when the system under investigation undergoes no net photochemistry and exhibits only
minimal structural change upon photoexcitation. While this assumption might appear to
cover the majority of our systems of interest, the possibility that AVr might contribute to
the observed LIOAS signal must be recognized and anticipated.
§ a is also referred to as p, the cubic expansion coefficient.

43
Instrument Design and Calibration Studies
Time-Resolved Thermal Lensing
An apparatus was set up to study TRTL with various organic and inorganic
systems of interest in our group. Before experimentation was undertaken, initial
calibration studies were first performed on the TRTL apparatus involving the triplet
excited-state energy measurement of various organic molecules and studying two
previously investigated donor-acceptor systems that are described below.
Apparatus setup
A diagram of the final apparatus is shown in Figure 2-10. The third harmonic of a
Nd:YAG laser (355 nm, Spectra-Physics GCR-14) is used as the pump beam, which is
attenuated with neutral density filters to an energy of approximately 100 - 200 pJ pulse'1.
This pump beam is directed through a plano-convex focusing lens that is mounted on a
two-axis positioning stage to simplify beam alignment. The focus of the pump beam is
generally in the center of the sample cell, although its position is tweaked using the
positioning stage to give the cleanest TRTL signal. A 1 mJ frequency-stabilized CW
He-Ne laser (633 nm, Aerotech 100-SF) is used as the probe beam, which is expanded
through two lenses to double the beam radius. The ratio of probe to pump beam radius in
our apparatus is 10:1. The expanded probe beam is directed through a plano-convex
focusing lens so that the focus of the beam is 10 cm in front of the cell based on the
Berthoud study.79 The probe and pump beams are combined in a colinear and concentric
fashion with the use of a 50% reflecting 633 nm beam splitter. The beams travel through
a 1 cm pathlength quartz sample cell and are then separated by the use of a dispersing

44
prism. The probe beam continues through a shutter to a pellicle beam splitter, which
reflects 8% of the beam through a plano-convex focus lens, an OG-590 cutoff filter,
diffuser (to minimize any possible position dependency of the PMT detector), and a 633
run interference filter before being detected with a R446 PMT. This PMT serves as the
experiment reference signal, which should correct for any transient absorption seen in the
excited sample. The remaining bulk of the probe beam travels 2.5 m until it reaches a
1.19 mm diameter pinhole. The center of the probe beam travels through an OG-590
cutoff filter and a 633 nm interference filter before being detected with a 1P28 PMT.
This PMT serves as the experiment sample signal.
The two PMT signals are simultaneously recorded on a Tektronix TDS 540 digital
oscilloscope using a 10 Hz sampling rate, with typically 1000 laser shots averaged during
each data collection cycle. The PMT signals are internally terminated (50 Q) with a 20
MHz internal bandwidth filter to reduce signal noise. The two decay traces are fed into
an analysis program written by the author in Microsoft Visual Basic 6.0, where the two
individual signals are initially normalized on a scale of 0 to 1. The normalized reference
signal is then subtracted from the normalized sample signal as specified in (2-5) to give
the observed TRTL signal, which is renormalized for final presentation to the user.

32.3
45
9
Table 2 M
Key:
1. Right Angle Prism
2. ND Filter
3. Plano-Convex Pump
Focus Lens (f = 75.5)
4 UV Coated Mirror
5. Plano-Convex Probe
Expander Lens 1 (f = 5.0)
6. Plano-Convex Probe
Expander Lens 2 (f = 10.1)
7. Plano-Convex Probe Focus
Lens (f = 35.0)
8. 632.8 nm Beam Splitter
9. Beam Dump
10. Sample Cell
11. Dispersing Prism
12. Shutter
13. 8% Reflecting Pellicle
Beam Splitter
14. Reference PMT Diffuser /
Plano-Convex Focus Lens
(f = 10.0)
15. Reference PMT
16. Standard Mirror
17. Standard Mirror
18. Pinhole
19 Signal PMT
Table 1
Figure 2-10: TRTL apparatus layout (all dimensions in cm).
Calibration studies
Initial TRTL work involved the triplet energy measurement of several common
organic triplet sensitizers in both polar and non-polar nitrogen-degassed solutions using
ssc) b»aW

46
(2-7). Benzophenone, phenanthrene, anthracene, and 9-methylanthracene were selected
as the triplet sensitizers. Unfortunately, triplet energies obtained with our instrument
failed to agree well with literature values for all the sensitizers except benzophenone.
Errors as high as 50% were obtained in some cases. The ineffective TRTL measurement
of these energies could stem from the rapid (several ns) excited-state decay of these
sensitizers, which is well below the sample acoustic transit time (200 ns). Furthermore, a
recurring problem with our apparatus involved obtaining a pure reference signal from the
reference PMT, where it was very common to see some evidence of thermal lensing. The
typical cure for bad reference signals was a careful adjustment of the probe and pump
beam geometries in the sample cell so that a good signal was recorded by the sample
PMT while as clean a reference signal as possible was recorded by the reference PMT. It
was not uncommon to obtain only one "good" experimental run during an hour of
constant measuring, as the beam positioning slowly drifted over time. While this trial-
and-error method was time consuming and tedious, it was the only effective way to
achieve reasonable data.
A second calibration study involved the use of donor-acceptor systems that had
considerably longer-lived excited states. Both tris(2,2’-bipyridine)Ru11 / methyl viologen
(MV2+)40,89 and (2,2’-bipyridine)Rel(CO)3(4-benzylpyridine)+ / diaza[2.2.2]octane
(DABCO)90’91 were studied with a significantly higher degree of success than the organic
triplet sensitizers. The excited state processes of the ruthenium / viologen system is
illustrated in Figure 2-11.

47
Free Ions
Figure 2-11: Ruthenium / viologen donor-acceptor system.
The Usiow
U
calculation for this system can be greatly simplified by making the paraquat
Total
concentration high enough to effectively quench all ruthenium emission (i.e., in Figure
2-11, ®em = 0 and ®q = 1). It is also assumed that the intersystem crossing yield (®jsc) is
U<
unity.76 The
Slow
u
calculation is now straightforward, as shown in (2-13).
Total
Usiow _ ^sepEpi
U
(2-13)
Total
'hu
If previously determined values for ®sep (0.31) and EFi (free ion energy; 1.69 eV = 2.7 x
10'19 J molecule'1) are used, the expected ^slow ratio is 0.15.40’89
U Total
Our ruthenium / paraquat measurements obtained a —ratio of 0.20, which had
U Total
a lower error than the organic triplet sensitizer measurements. Furthermore, our rhenium
/ DABCO measurements, which would exhibit the same behavior described in Figure

48
2-11,90,91 almost exactly matched the predicted results (0.41 predicted; 0.42
experimentally determined). Eventually, TRTL was abandoned for LIOAS when the
excessively tedious process to correct for sample transient absorption proved to not be
worth the uncertain results obtained with our apparatus. However, our TRTL apparatus
was successfully used for the triplet energy determination of polymer PI, which is
described in chapter 3.
Laser-Induced Optoacoustic Spectroscopy
Apparatus setup
The layout for our LIOAS apparatus is illustrated in Figure 2-12. The
instrumental demands for LIOAS are straightforward compared to TRTL. A pellicle
beamsplitter diverts 8% of the 355 nm Nd:YAG radiation (Spectra Physics GCR-14)
through a stack of neutral density filters (typically 10% and 25% ND filters are used). A
very low excitation energy (8 - 40 pJ pulse'1) is required in LIOAS studies to prevent
multiphoton events. The remaining portion of the pump beam is sampled with an energy
meter (Scientech S310 with a P09 Probe) to allow for energy normalization. After
passing through a 2 mm slit to minimize beam wandering effects, the pump beam is
focused with a plano-convex lens (f = 10.0 cm), producing a beam diameter of 0.25 mm
within the sample cell. The transducer is held to the side of the sample cuvette
perpendicular to the pump beam propagation by means of an in-house designed cell
holder. A film of vacuum grease is applied between the transducer and cell wall to better
facilitate the relay of acoustic waves. The cell holder is mounted on a linear translation
stage to allow variation of the excitation region distance from the transducer surface
within the sample. Varying this distance allows for temporal movement of the transducer

49
response from any initial laser RF noise. Since the cell / transducer geometry cannot
change between reference and sample experiments, the cell is firmly clamped in place and
a solvent delivery system is constructed to distribute rinsing solvent, nitrogen purging
gas, and sample solutions without moving the cell. The sample cell was typically rinsed
with flowing solvent for 5 minutes and dried with flowing nitrogen gas between
experiments.
Figure 2-12: LIO AS apparatus layout.
Two transducers are used with differing characteristic frequencies, 1 MHz
(Panametrics VI03) and 5 MHz (Panametrics VI09). The higher frequency transducer
should be more sensitive to shorter-lifetime excited-state processes. The signals are
intensified with a Panametrics 5670 40 dB preamplifier and recorded with a Tektronix
TDS 540 digitizing oscilloscope. Initial data processing, instrument control and data
normalization are conducted with software written in Microsoft Visual Basic 6.0 by the
author. Sound Analysis 3000 software is used to deconvolute the processed acoustic

50
Q9
waves and provide amplitudes and lifetimes. Pictures of the LIO AS apparatus are
shown in Figure 2-13.
Calibration study - (b)ReI(CO)3(bzpy)+ triplet energies
A detailed LIOAS calibration study was conducted to determine the triplet
metal-to-ligand charge transfer (3MLCT) energy of a series of rhenium complexes, fac-
(b)ReI(CO)3(bzpy)+, where b is a substituted diimine ligand and bzpy is 4-benzylpyridine
(Figure 2-14). This inorganic chromophore has been widely studied, and its
photophysical properties are well known. Furthermore, the MLCT energy is easily
varied over several kcal mol'1 by changing the substituted diimine.41,42 Since the
(b)Re*(CO)3(bzpy)+ 3MLCT state is emissive, its spectrum can serve as a second
independent means of measuring its energy through Franck-Condon emission lineshape
fitting.76,91 The series of complexes also has different 3MLCT lifetimes due to their
varying excited state energies, so the delineation between fast, intermediate, and slow
lifetime processes detected by our LIOAS apparatus can be studied and confirmed.
The 3MLCT Energy. The 3MLCT energy for the (b)Re(CO)3(bzpy)+ complexes,
along with other emissive transition metal complexes, is traditionally determined with a
single-mode Franck-Condon line-shape analysis of the observed 3MLCT emission band
observed at ambient temperature.76,91 Therefore, experimental emission spectra for the
complexes obtained from nitrogen-degassed acetonitrile solutions were fitted to (2-14).
w-Z
v„=0
Í V00-Vm^m^
3(sJb-
-4 In 2
"v-v00+vm/icDm^
2"
-
1 P
k AV0,l/2 ,
V voo )
vm!
(2-14)

51
Laser Energy
Meter Probe
Transducer
Pellicle Beam Splitter
(8% R) 2 mm Slit
10&25%T^r
Figure 2-13: LIOAS apparatus images

52
R,
VN/.
N'
R
R,
CO
(b) = (tmb): R! = CH3, R2= CH3
vxCO
(b) = (dmb): R1 = H, R2=CH3
Re'
(b) = (bpy): R1 = H, R2 = H 0
>
^co
(b) = (damb) R, = H, R2 = /U'NE<2
1
(b) = (deb): R, = H, R2 = OEt
Figure 2-14: (b)Re(C0)3(bzpy)+ complexes.
In (2-14), l(v) is the relative emission intensity at energy v , v00 is the zero-zero
transition energy (i.e., the 3MLCT energy), vm is the average medium frequency
vibrational mode quantum number, heom is the medium frequency acceptor modes
average coupled to the MLCT transition (1450 cm"1),76 Sm is the Huang-Rhys factor (i.e.,
the electron-vibration coupling constant), and Av01/2 is the individual vibronic band
half-width. The v00 values obtained from (2-14) for the (b)Re‘(CO)3(bzpy)+ series are
listed in Table 2-1, and fitted emission spectra are shown in Figure 2-16 along with the fit
parameters. These fit parameters are consistent with a previous study conducted in our
group on similar complexes.91

53
Table 2-1: Emission data for (b)Re'(CO)3(bzpy)+.
(b)a
^em
^em / US
v0o/cm-,c
(kcal mol'1)
tmb
0.25
1473
18700
19400
dmb
0.06
274
17450
(55.5)
18375
bpy
0.045
208
17210
(52.5)
17975
damb
0.026
116
16700
(51.4)
17280
deb
0.0145
93
15360
(49.4)
16050
(45.9)
“Argon-degassed CH3CN solutions, 298 K. Estimated errors: em, ± 15%; Tem, ± 5%; , ± 100 cm'1;
v00, ± 500 cm'1. bEmission maximum. c0-0 emission energy estimated by Franck-Condon analysis (2-14).
Since the 3MLCT excited state lifetime for the (b)Re’(CO)3(bzpy)+ complexes
falls within the medium lifetime category of LIOAS responses, the energy of the lowest
MLCT excited state can be independently calculated from both of the two expected
components recovered from the LIOAS data deconvolution analysis. In principle, the
first “fast” heat deposition process (xi and i) corresponds to heat released when the
singlet MLCT state (*MLCT, the excited state produced by photon absorption) relaxes to
3MLCT with unit efficiency. The second heat deposition process (i2 and 2) corresponds
to heat released concomitant with nonradiative decay of 3MLCT. Based on these
definitions, the amplitudes can be related to the 3MLCT energy by (2-15) and (2-16).
4>i =Eh:~ET (2-15)
Ehv
<1)2 = Et(i—q>em)
(2-16)

54
In (2-15) and (2-16), Ehv is the excitation energy (355 nm = 80.5 kcal mol'1), Oem
is the emission quantum yield from 3MLCT and Ey is the 3MLCT energy. LIOAS decays
were obtained from degassed acetonitrile solutions with both the 1 MHz and 5 MHz
ultrasonic transducers of each complex in the (b)Re(CO)3(bzpy)+ series. Figure 2-15
illustrates typical analysis results for the (b)Re'(CO)3(bzpy)+ series. Table 2-2 contains
the average normalized amplitudes (i) recovered from deconvolution analysis of four
independent LIOAS measurements on each complex, the lifetime of the medium lifetime
heat-deposition component (12), and Ey values calculated from the experimental j values
with (2-15) and (2-16). Figure 2-16 shows the emission spectra and compares 3MLCT
energies for the five (b)Re(CO)3(bzpy)+ complexes obtained from the LIOAS data using
both transducers (four Ey values for each complex) and the emission Franck-Condon
analysis.
The Validity of LIOAS Measurements Several assumptions must be made in order
to assess the potential use of LIOAS data for the determination of excited state energies.
First, the emission spectra and Franck-Condon bandshape analysis is assumed to provide
the best available estimate for the 3MLCT energy, which is less than ideal due to the
convoluted mathematical fit. However, since this methodology is widely accepted in the
literature it is deemed sufficient for a yardstick in evaluating the LIOAS technique for this
purpose. Second, our LIOAS data analysis neglects contributions to the acoustic wave
arising from the potential volume change that occurs concomitant with 3MLCT decay as
discussed earlier.

55
Figure 2-15: LIOAS data (signal vs. time) for (b)Re(CO)3(bzpy)+ in acetonitrile. Solid
(highest intensity) lines are the ferrocene reference waveform, dotted lines are the sample
waveform, and dashed lines are the deconvolution fit. Note that n = 10 and 1 ns for the 1
and 5 MHz transducers, respectively.

56
Figure 2-15 - Continued
Three major conclusions can be drawn concerning the measurement of excited
state energies and lifetimes using the LIOAS apparatus and deconvolution analysis.
1. LIOAS Measurements are accurate only when the excited state lifetime is
greater than 200 ns. It can clearly be seen in Figure 2-16 that for the complexes with
tmb, dmb, and bpy ligands, the 3MLCT energies derived from LIOAS and emission
spectral fitting are in reasonable agreement. In stark contrast, the LIOAS energy values
for complexes with damb and deb ligands vary widely and are in poor agreement with the
emission spectral fitting energies. The 3MLCT lifetimes of the three complexes with

57
concurrent energy measurements range from 210 to 1500 ns, while the two disparate
complex lifetimes range from 90 to 120 ns (see xem in Table 2-1 and the X2 deconvolution
component in Table 2-2). This result clearly indicates that the validity of the LIOAS data
is strongly influenced by the probed excited state lifetime, and the lower lifetime limit for
reliability with our apparatus is x > 200 ns. This limit is directly related to the acoustic
transit time (xa) of the LIOAS apparatus as defined above. If a beam radius of 0.25 mm
and a velocity of sound in acetonitrile of 1300 m s’1 is assumed for our instrument, an
acoustic transit time of 192 ns is obtained. This acoustic transit time is not small enough
to accurately resolve the fast relaxation of the 1MLCT state and the nonradiative decay of
the MLCT state for complexes with MLCT lifetimes less than 200 ns (i.e., the damb
and deb complexes).
2. Excited state energies derived from deconvolution of the second medium
lifetime deconvolution component are less precise and accurate compared to those
derived from the first fast lifetime deconvolution component. The error bars shown in
Figure 2-16 clearly indicate that the precision and accuracy of the energies determined
from (j>2 and (2-15) are generally poorer compared with those derived from 4>i and (2-16).
Simulated LIOAS responses derived by reconvolution of two decay components similar
to those observed for (b)Re'(CO)3(bzpy)+ indicate that (j>i is primarily influenced by the fit
quality in the initial spike of the LIOAS signal, while 2 is determined mainly by the fit
quality in the subsequent LIOAS signal oscillations after the initial peak. This secondary
oscillation region of the LIOAS signal is complex and relatively noisy in our recorded
LIOAS data, which inherently decreases the precision of the fitted 2 values.

58
Table 2-2: LIO AS data for (b)Re1(CO)3(bzpy)+.
1 MHz Transducer
Ligand3
i
t2 / ns
Et / cm'1 b
(kcal mol'1)
Et / cm'1 £
(kcal mol'1)
tmb
0.2698 ± 0.02
0.4402 ± 0.05
1109 ±294
20570 ± 630
16540 ± 1850
dmb
0.3281 ±0.02
0.6267 ± 0.09
264 ± 11
(58.8 ± 1.8)
18610 ± 450
(47.3 ± 5.3)
18780 ±2550
bpy
0.3059 ± 0.04
0.6410 ±0.01
196 ±9
(53.2 ± 1.3)
19550± 1110
(53.7 ±7.3)
18890 ±420
damb
0.3534 ±0.08
0.5908 ± 0.06
103 ±6
(55.9 ±2.9)
18220 ±2310
(54.0 ± 1.2)
17070± 1750
deb
0.3070 ± 0.02
0.6493 ± 0.07
56 ± 9.7
(52.1 ±6.6)
19520 ±700
(48.8 ± 5.0)
18540 ±2100
(55.8 ±2.0)
(53.0 ±6.0)
5 MHz Transducer
Ligand3
i
2
x2 / ns
Et / cm 1 b
(kcal mol'1)
ET/cmlc
(kcal mol'1)
tmb
0.3122 ±0.03
0.5123 ±0.04
772± 180
19380 ±730
19240± 1400
dmb
0.3486 ± 0.04
0.6302 ± 0.03
249 ± 17
(55.4 ±2.1)
18360 ±1010
(55.0 ±4.0)
18890 ±870
bpy
0.3587 ±0.04
0.6780 ± 0.05
197 ± 14
(52.5 ±2.9)
18050±1150
(54.0 ±2.5)
20010± 1430
damb
0.4238 ± 0.03
0.5475 ± 0.04
111 ±6
(51.6 ±3.3)
16230 ±910
(57.2 ±4.1)
15840 ±1120
deb
0.5156 ± 0.12
0.5499 ±0.10
79 ± 9.5
(46.4 ± 2.6)
13640 ±3360
(45.3 ± 3.2)
15700 ±2800
(39.0 ±9.6)
(44.9 ± 8.0)
“Argon-degassed CH3CN solution, 298 K. Reported values are averages of four runs of fresh sample and
ferrocene reference solutions, and errors are ± a. t, fixed at 10 ns for the 1 MHz transducer and 1 ns for the
5 MHz transducer. bTriplet energy calculated from the first deconvolution amplitude (2-15). 'Triplet
energy calculated from the second deconvolution amplitude (2-16).

59
V)
'E
Z)
£
re
k.
V
!5
k.
<
W
C
c
o
(O
E
LU
TJ
0)
N
re
E
k-
o
z
12
14 16 18
Emission Energy /103 cm 1
20 22 24
• Emission u00
A LIOAS 4», , 1 MHz
A LIOAS , 1 MHz
O LIOAS <*>, , 5 MHz
♦ LIOAS <)>2,5 MHz
Figure 2-16: Corrected emission spectra of (b)Re‘(CO)3(bzpy)+ in acetonitrile solution at
298 K. Points are experimental data, and solid lines are spectra calculated using Franck-
Condon analysis (2-14) with the fitting parameters listed on each spectrum. 3MLCT
energies are presented on each plot with ± a errors, (a) b = (tmb); (b) b = (dmb);
(c) b = (bpy); (d) b = (damb); (e) b = (deb).

60
3. Lifetimes can be accurately measured with LIO AS for medium lifetime
decay processes. It is clearly seen in Tables 2-1 and 2-2 that the 3MLCT lifetime
independently obtained by LIOAS and emission measurements is in reasonable agreement
for the complexes with dmb and bpy ligands. These complexes represent the medium
lifetime processes that are correctly measured by the transducer. For a slow lifetime
process (i.e., the tmb complex) the transducer detected a signal that is partially damped by
the transducer, resulting in an erroneously low lifetime. This damping increases for the 5
MHz transducer due to its higher characteristic oscillation, which leads to the larger
observed errors. The narrow range of lifetimes correctly measured by LIOAS suggests
that traditional (e.g., optically-based) methods are more suitable for determining these
values.
This calibration study demonstrates the validity of LIOAS measurements to
measure excited state energies and lifetimes so long as the excited-state lifetime is higher
than the acoustic transit time of the apparatus (ca. 200 ns). LIOAS will be further used to
determine the triplet energies and/or yields of several rr-conjugated oligomers and
inorganic complexes discussed in chapters 3 and 5.
Experimental
(b)ReI(CO)3(bzpy)+ Synthesis
Synthesis of (b)Re'(CO)3CI. This synthesis proceeded via analogous procedures
for each complex, so a representative procedure is given. For (4,4',5,5'-tetramethyl-2,2'-
bipyridine)Re'(CO)3Cl, 300 mg of Re(CO)sCl (0.833 mmol, prepared by literature
method),94 194 mg 4,4',5,5'-tetramethyl-2,2'-bipyridine (tmb, 0.916 mmol, 1.1

61
equivalents), and 15 mL toluene were placed in a roundbottom flask. The solution was
stirred and refluxed under nitrogen for 1.5 hours, during which time the off-white
solution turned a golden yellow. A yellow precipitate formed, and the mixture was stirred
at room temperature under nitrogen overnight to complete the reaction. The precipitate
was filtered with a medium porosity glass frit, washed with three toluene washes, and
dried under vacuum for several hours to remove excess toluene. 400 mg of
(tmb)Re'(CO)3Cl was collected (93% yield). The remaining complexes were synthesized
with similar yields.
Synthesis of (b)Re1(CO)3(bzpy)+. The synthesis of each complex is similar for
the entire series, so extensive details are only given for the (tmb)Re'(CO)3(bzpy)+
complex. All other complexes were synthesized with analogous procedures but varying
reaction times.
[(4,4',5,5,-tetramethyl-2,2'-bipyridine)ReI(CO)3(bzpy)][OTf]. In a
roundbottom flask 200 mg of (tmb)Re‘(CO)3Cl (0.386 mmol) and 124 mg silver triflate
(0.425 mmol, 1.25 equivalents) were dissolved in 15 mL methylene chloride. The
solution was stirred in the dark at room temperature overnight to complete the
counteranion exchange. A dark yellow solution resulted with a fine white silver chloride
precipitate. The precipitate was removed by filtration through celite on a medium
porosity glass frit. The filtrate was placed in a clean roundbottom flask, and 185 mg of 4-
benzylpyridine (1.16 mmol, 3 equivalents) was added while the solution stirred. The
solution was stirred at room temperature for 24 hours, during which time its luminescence
dramatically increased when excited with UV light. A dull yellow precipitate was
obtained after rotary evaporation of the solvent, which was washed twice with ether and

62
dried under vacuum. A light yellow powdery precipitate, [(tmb)Re’(CO)3(bzpy)][OTf],
resulted (52 mg, 17% yield). 'H NMR (CDC13) 6 2.40 (s, 6H, methyl), 2.56 (s, 6H,
methyl), 3.91 (s, 2H, benzylic), 7.10 (d, pyridyl), 7.20 - 7.40 (m, phenyl), 7.93 (s, tmb),
7.98 (d, pyridyl), 8.57 (s, tmb).
[(4,4'-dimethyl-2,2'-bipyridine)Rel(CO)3(bzpy)][OTf|. A yellow powdery
precipitate, [(dmb)Re'(CO)3(bzpy)][OTf], resulted (89% yield). 'H NMR (CDCI3) 5 1.60
(s, 6H, methyl), 3.90 (s, 2H, benzylic), 7.10 (d, 2H, pyridyl), 7.20 - 7.40 (m, phenyl), 7.52
(d, 2H, dmb), 7.92 (d, 2H, pyridyl), 8.70 (s, 2H, dmb), 8.82 (d, 2H, dmb).
|(2,2'-bipyridine)Rel(CO)3(bzpy)][OTf]. A bright yellow crystalline precipitate,
[(bpy)Re'(CO)3(bzpy)][OTf], resulted (62% yield). *H NMR (CDC13) 6 3.90 (s, 2H,
benzylic), 7.09 (d, pyridyl), 7.20 - 7.40 (m, phenyl), 7.78 (dd, 2H, bpy), 8.00 (d, 2H,
pyridyl), 8.35 (d, 2H, bpy), 8.95 (dd, 2H, bpy), 9.03 (d, 2H bpy).
[(4,4'-bis(diethylamino)-2,2'-bipyridine)Rel(CO)3(bzpy)][OTfl. A dark yellow
crystalline precipitate, [(damb)Re'(CO)3(bzpy)][OTf], resulted (50% yield). ‘H NMR
(CDCI3) 5 1.21 (t, methyl), 3.47 (qq, methylene), 3.92 (s, 2H, benzylic), 7.08 (d, pyridyl),
7.10 - 7.40 (m, phenyl), 7.59 (d, damb), 8.12 (d, pyridyl), 8.42 (s, damb), 9.01 (d, damb).
[(4,4',5,5'-diethoxy-2,2'-bipyridine)Rel(CO)3(bzpy)][OTfj. A dark red
crystalline precipitate, [(deb)Re'(CO)3(bzpy)][OTf], resulted (low yield, but it was the
most difficult by far to synthesize). ‘H NMR (CDC13) 1.48 (t, 6H, methyl), 3.88 (s, 2H,
benzylic), 4.55 (q, 4H, methylene), 7.09 (d, pyridyl), 7.20 - 7.40 (m, phenyl), 8.09 (d, 2H,
pyridyl), 8.27 (d, 2H, deb), 8.98 (s, 2H, deb), 9.24 (d, 2H, deb).

63
(b)Re(CO)3(bzpy)+ Photophysics
Steady-state emission spectroscopy and emission quantum yields. Corrected
steady-state emission spectra were recorded on degassed acetonitrile solutions of each
complex with a SPEX F-l 12 fluorimeter. Samples were contained in 1 cm x 1 cm quartz
cuvettes and excited at 350 nm. Emission quantum yields (Oem) were calculated relative
to two actinometers using (2-17).9:>
Ox = 0r
em em
^ i—10~Af
1-10“A‘
Y«2Vp '\
fir )
V^ry
(2-17)
In (2-17), x represents properties of the unknown solution and r represents properties of
the actinometer, A is the sample solution absorbance at the excitation wavelength, q is
the sample solvent refractive index, and D is the area under the emission band. Run(bpy)3
in degassed water (Oem = 0.055)96 and 9,10-dicyanoanthracene in ethanol (Oem = 0.89)97
were used as actinometers. All solution concentrations were adjusted to result in
optically dilute solutions (A3sonm = 0.14).
Emission Lifetimes. Time-correlated single-photon counting (FLI,
Photochemical Research Associates) was used to measure emission lifetimes. The
excitation and emission wavelengths were selected with bandpass filters (excitation,
Schott UG-11 (350 nm maximum); emission, 550 nm interference filter). Degassed
acetonitrile samples were contained in 1 cm x 1 cm quartz cuvettes. Lifetimes were
calculated from single-exponential fits with the DECAN fluorescence lifetime
OR
deconvolution software.
LIOAS Measurements. LIOAS measurements were conducted on acetonitrile
samples with the apparatus described above. Before each experimental run, a linearity

64
test was performed with the ferrocene reference to determine the maximum usable laser
energy while maintaining linearity. Based on these tests, laser energies of 2 and 20 pj
pulse'1 were used for the 1 and 5 MHz transducers, respectively. Four experimental
cycles were performed for each compound and averaged, with each cycle consisting of
fresh ferrocene reference solution and (b)Re‘(CO)3(bzpy) solution measurements. Each
measurement was the average of acoustic waveforms collected from 1000 laser pulses at
a 10 Hz repetition rate. All samples were nitrogen degassed in the fixed LIOAS cell for
20 minutes before data acquisition.
Deconvolution analysis was performed with the two-component sequential step
model. Lifetimes for the fast decay component were fixed at 10 and 1 ns for the 1 MHz
and 5 MHz transducers, respectively, while the other fit parameters were allowed to float.
For the 1 MHz transducer data, only a background correction was necessary to achieve
the desired fit, but the narrower bandwidth of the 5 MHz transducer data required both
background and reference shift correction factors in the final deconvolution process.

5-5' BIPHENYL OLIGOMER PHOTOPHYSICS
Introduction
As discussed earlier, a series of oligomers (5-L series) was synthesized containing
biphenyl subunits in the conjugated backbone. The oligomers contain a 5,5’-(2,2’-
bipyridyl) core with primary repeat units on either side consisting of 5,5’-diethynyl(2,2’-
biphenyl) and dialkoxybenzenes. These oligomers were synthesized via Sonogashira
coupling, an iterative sequence involving palladium-mediated cross coupling of a
terminal acetylene and aryl iodide.64,99 Complexes were synthesized by ligating these
oligomers to the -Re^CO^Cl (5-Re series)99,100 and -Re‘(CO)3(NCCH3)+ (5-ReAN-2
and 5-ReAN-3 complexes) chromophores. The structures of the 5-L oligomers and 5-Re
complexes are shown in Figure 3-1. Extensive photophysical and photo thermal studies
were conducted on these molecules, and the results are presented in this chapter.
Results
Various photophysical parameters from many different measurements are
presented for the uncomplexed 5-L oligomers and 5-Re rhenium complexes in Tables 3-1
and 3-2, respectively. The individual measurements are discussed below. For
comparative purposes, some of the photophysical data collected for polymers PI and P4
described in chapter 1 (Figure 1-15) are also presented.
65

66
5-L-1: M = -
5-Re-1: M = Re'(CO)3CI
Y
5-L-2: M = -
5-Re-2: M = Re'(CO)3CI
5-ReAN-2: M = Re'(CO)3(NCCH3)+OTr
/==V
//
RO
---
RO
RO A/
5-L-3: M = -
5-Re-3: M = Re'(CO)3CI
5-ReAN-3: M = Re'(CO)3(NCCH3)+OTr
OR OR
RO RO
5-L-4: M = -
5-Re-4: M = Re'(CO)3CI
OR
-S
R = Ci8H37
Figure 3-1: 5-L oligomer and 5-Re rhenium complex structures.
Table 3-1: 5-L oligomer photophysics.
5-L-l
5-L-2
5-L-3
5-L-4
Absorption
^-max / nm
330(3.85)
320 (6.90)
340 (9.05)
336(15.2)
(emax/104 M'1 cm'1)
370(5.40)
400 (9.80)
404(13.5)
406 (25.1)
Emission
^max, 298 K / nm
455
454
453
452
^max, 80 K / nm
413
469
482
496
^em
0.89
0.72
0.68
0.79
TA
^298 K / M-S
158
452
343
411
Note: Measurements were conducted on argon bubble-degassed THF solutions. Additional experimental
conditions are discussed in the text.

67
Table 3-2: 5-Re rhenium complex photophysics.
5-Re-l
5-Re-2
5-Re-3
5-Re-4
Absorption
X^ax/nm
332 (2.90)
336 (8.30)
352 (11.8)
338 (16.8)
(emax/104 M'1 cm'1)
410(3.40)
440 (7.34)
444 (8.30)
388 (20.7)
444(10.3)
Emission
7-max, 298 K / I'm
690
650
652
650
7â„¢x,80ic/nm
586
659
642
642
TA
^298 K / OS
20
145
198
161
Electrochem
E[e/d2 /V vs. SCE
-0.89a
-0.87a
-0.86a
-0.918,0
-0.90b
-0.92b
-0.85bc
Note: Measurements were conducted on argon bubble-degassed THF solutions. Additional experimental
conditions are discussed in the text. aPt disc working electrode. bGCE disc working electrode, irreversible
reduction.
5-ReAN-2
5-ReAN-3
Absorption
Aqnax / nm
340 (9.49)
348 (14.7)
(emax/104 M'1 cm’1)
449(7.38)
447 (9.49)
Emission
Tmax, 298 K / nm
652
650
7-max, 80 K / nm
589, 625
629
TA
^298 K / OS
9710
5010
Note: Measurements were conducted on argon bubble-degassed THF solutions (except for transient
absorption measurements, which are conducted in methylene chloride). Additional experimental conditions
are discussed in the text.
Absorption Spectra
Absorption spectra were obtained on dilute THF solutions of the various
oligomers and rhenium complexes, and molar absorptivity values (e, M'1 cm'1) were
calculated based on (3-1).
A = ebc
(3-1)

68
In (3-1), A is the sample absorbance, b is the cell pathlength (1 cm), and c is the sample
concentration (M). Absorption spectra for the 5-L and 5-Re series, along with PI and
P4, are shown in Figure 3-2. Absorptivity for PI was calculated based upon the polymer
repeat unit. Absorptivity calculations were not performed on P4. Absorption maxima for
all oligomers and rhenium complexes are listed in Tables 3-1 and 3-2, respectively.
The oligomer spectra exhibit two n,n* transitions, with the lower energy (HOMO
-» LUMO) transition corresponding to a long-axis polarized transition and the higher
energy transition corresponding to a perpendicular short-axis transition. The low-energy
band red-shifts to lower energies from 5-L-l to 5-L-2. However, further shifting does not
readily occur as the oligomer size increases from 5-L-2 to 5-L-4. This observation
suggests that the effective conjugation length (i.e., oligomer “bandgap”) is reached
relatively early in the series. Note the similarity in the 5-L-4 and PI spectra, which are
similar to other reported PPE-type oligomer and polymer absorption spectra (Figure
1-4).5’26,101'103 The oligomer bands are blue-shifted compared to PPE (Figure 1-4) due to
the incorporation of the bipyridine and biphenyl subunits, which is analogous to the
bipyridine-containing BEH-PPV blue-shift discussed in chapter 1.

69
o
o
c
m
.o
o
w
S3
<
E
o
co
o
co
Figure 3-2: Absorption spectra in THF. (a) 5-L oligomers and PI; (b) 5-Re complexes
and P4; (c) 5-ReAN-2 and 5-ReAN-3 complexes.

70
While the 5-Re rhenium complex spectra exhibit at least two similar n,n*
transitions, a significant long-axis n,n* transition (HOMO —> LUMO) red-shift and
smaller short-axis transition red-shift in comparison to the free oligomer spectra is
observed. The energy of the low-energy band remained fairly constant in the complexes,
while the high-energy band continues to red-shift with increasing oligomer length. This
feature suggests that for 5-Re-2 - 5-Re-4 the low-energy band is associated with a
“constant” chromophore, while the higher energy band arises from a separate “varying”
chromophore that is dependent on the oligomer length. The implications of this
observation are discussed later. Note that the molar absorptivities are considerably higher
than expected for any MLCT-based absorptions,104 so it is believed that these absorptions
are “buried” under the more intense oligomer 71,71* transitions. Also, the 5-Re-4 and P4
spectra are very similar, suggesting that the oligomers readily reflect the polymer
photophysics.
Emission Spectra
Emission spectra of the 5-L oligomers in optically dilute 2-methyltetrahydrofuran
(2-MTHF) solutions at temperatures ranging from room temperature to 80 K are shown in
Figure 3-3. Emission maxima at room temperature and 80 K are listed in Table 3-1. The
oligomer fluorescence spectra at room temperature feature a strong band that exhibits a
small Stokes shift (i.e., shift to lower energies) from the lowest-energy absorption. On
this basis, the emission is assigned to the long-axis polarized *71,7:* state. This
fluorescence is very similar in energy and bandshape to related PPE (Figure 1 -4) and PPV
7r-conjugated polymers and oligomers, including PI.1,21,26,46,105-107 The fluorescence

71
maximum did not vary significantly throughout the oligomer series. Therefore, the '71,71*
excited-state energy essentially remained constant upon variation of the oligomer length,
which mirrors the lack of variation in the lowest-energy absorption band maximum.
Comparison of the oligomer fluorescence spectra reveals that the spectral bandwidth
decreases with increasing oligomer length. In addition, a clear trend emerges for
oligomers 5-L-2 - 5-L-4 as the intensity of the (0,1) shoulder decreases relative to the
(0,0) maximum with increasing oligomer size. These observations signal that the
electron-vibration coupling in the '71,71* state decreases with increasing oligomer length
due to greater '71,71* state delocalization. This decrease suggests that the excited state is
less “distorted” upon photoexcitation, possibly due to the increased steric bulk of the
alkyl chains as the oligomer size increases. A similar fluorescence trend was observed by
Becker and coworkers for a series of oligothiophenes, and they suggested a similar
conclusion.29 No phosphorescence was detected at low temperatures for any of the 5-L
oligomers or PI. This observation for the polymers is not terribly surprising, as the
presence of defect sites or “exciton traps” would provide a nonradiative decay route,
consequently excluding the observation of phosphorescence.
The oligomer fluorescence red-shifted with decreasing temperature, and at the
lowest examined temperatures for all of the oligomers (except 5-L-l) the emission was
dominated by a broad band at a lower energy than the assigned room temperature (0,0)
band. A corresponding thermochromism was seen in the lowest-energy '71,71* absorption
band for 5-L-3 and 5-L-4 (data not shown). Excitation spectra for the oligomers
measured at different wavelengths on the emission band were generally indistinguishable,
suggesting that the states involved in the observed photophysics were in strong electronic

72
communication. Low temperature spectra of 5-L-l show a dramatic blue-shift below 110
K leading to a final structured spectra after exhibiting the red-shift seen in all other
oligomers at higher temperatures.
400 450 500 550 600 650
Wavelength / nm
Figure 3-3: Emission spectra of the 5-L oligomers in 2-MTHF (350 nm excitation) at
temperatures varying from 298 to 80 K. Emission intensity decreases as temperature
decreases, and spectra are in 20 K increments, (a) 5-L-l (note unusual low-temperature
trends); (b) 5-L-2; (c) 5-L-3; (d) 5-L-4.

73
Emission quantum yields were measured for the oligomers using (2-17), and
calculated values are listed in Table 3-1. The high emission quantum yield is typical of
rigid-rod ^-conjugated polymers and other rigid organic fluorophores.108 The quantum
yields decrease as the oligomer size increases (except 5-L-4), suggesting more efficient
intersystem crossing as the extended structure of the oligomer increases.
Polarized emission measurements were performed on oligomers 5-L-3 and 5-L-4
to further study the interesting thermochromism. Wavelength-resolved polarization
anisotropies (r(X)) were calculated with (3-2).109
rfr)= Iw-O^h (3.2.)
I vv + 2GIVH
G = ^-
Ihh (3-2b)
In (3-2), Ixy is the emission intensity with the excitation and emission polarizers adjusted
according to x and y, respectively (e.g., Ihv is the emission intensity with horizontally
polarized excitation light and vertically polarized emission detection). Anisotropy
measures the polarized light component ratio to its total intensity and is a direct indication
of the angle between absorption and emission dipoles, a. Anisotropy values vary from
0.4 (a = 0°) to -0.2 (a = 90°), with an anisotropy value of zero statistically representing
unpolarized light (e.g., a uniform statistical distribution of emitting dipole angles relative
to the absorption dipole).109
Emission spectra at room temperature and 170 K in 2-MTHF and calculated
anisotropies at these temperatures are shown in Figure 3-4, and the anisotropy
temperature dependence at 525 nm for both oligomers is shown in Figure 3-5. The 170 K

74
experiment temperature is slightly above the 2-MTHF freezing point, thus eliminating
solvent glass effects on the observed anisotropy. At 298 K, r(A.) is relatively constant
across the fluorescence band (r « 0.24) for both oligomers. With decreasing temperature
r(X) slightly increases on the blue side of the fluorescence band, but a sharp decrease on
the far red side of the band is observed for 5-L-3 at T < 190 K and for 5-L-4 at T < 230
K. The implications of these observations are discussed below.
0.5
0.4
0.3
0.2
0.1
0.0
0.5
0.4
0.3
0.2
0.1
0.0
0.5
0.4
0.3
0.2
0.1
0.0
0.5
0.4
0.3
0.2
0.1
0.0
400 450 500 550 600 650
Wavelength / nm
<<
'sr
Figure 3-4: Emission (dashed line) and emission polarization (solid line) r(>.) spectra
(350 nm excitation) in 2-MTHF. (a) 5-L-3, 298 K; (b) 5-L-3, 170 K; (c) 5-L-4, 298 K;
(d) 5-L-4, 170 K.

75
Figure 3-5: Emission anisotropy temperature dependence observed at 525 nm. Solid
circles are 5-L-3 data, and open circles are 5-L-4 data.
Emission spectra for the 5-Re complexes in optically dilute 2-MTHF solutions at
temperatures ranging from 298 to 80 K are shown in Figure 3-6. Emission maxima at
298 and 80 K are listed in Table 3-2. Although not shown, a weak emission was
observed in all the rhenium complex samples that matched the free oligomer ‘71,71*
fluorescence seen in Figure 3-3. This emission is two orders of magnitude smaller than
those observed for the uncomplexed oligomers. It is impossible to know whether this
fluorescence originates from the rhenium complexes or is a trace oligomer impurity in the
rhenium complex samples. Nonetheless, it is clear that the oligomer fluorescence is
strongly quenched by the MLCT chromophore.

76
Wavelength / nm
Figure 3-6: Emission spectra of the 5-Re complexes in 2-MTHF (440 nm excitation) at
various temperatures from 298 to 80 K. Emission intensity increases with decreasing
temperature, and spectra are in 20 K increments, (a) 5-Re-l; (b) 5-Re-2; (c) 5-Re-3; (d)
5-Re-4; (e) 5-ReAN-2; (f) 5-ReAN-3.
The rhenium complexes exhibited a weak, low-energy emission that increased
with decreasing temperature (about twenty-fold from 298 to 80 K). Spectra for 5-Re-l
evolved from a broad structureless 680 nm band at 298 K to a blue-shifted, highly
structured 586 nm band at 80 K. This thermally-induced emission energy shift exhibits
trends typically observed for (b)ReI(CO)3Cl 3MLCT emission.41 For the remaining

77
rhenium complexes, a 650 nm band was observed at 298 K with a poorly defined vibronic
structure, and a superposition of a structureless 600 nm band and a structured (0,0) 650
nm band with a vibronic (0,1) shoulder was obtained at 80 K. In general, there was very
little band shifting of the structured emission to higher or lower energies as the
temperature decreased for these complexes, and the observed band superposition “blurs”
as the oligomer size increases. Attempts to measure the luminescence quantum yields of
the 5-Re complexes were unsuccessful, as in each case the emission was too weak to be
effectively measured ( agree well with the absorption spectra, suggesting efficient electronic communication
between the n,n* oligomer and dn (Re) —> n* MLCT excited states.
In order to further probe the superimposed emission spectra at low temperatures,
excitation polarization studies were conducted at 80 K on 2-MTHF solutions of 5-Re-3
using various emission wavelengths. Excitation spectra and r(A.) values are shown in
Figure 3-7 along with an 80 K emission spectrum that indicates the examined
wavelengths. For the blue structureless shoulder of the emission spectrum, the anisotropy
value is high for the lowest-energy absorption band (0.3), which strongly suggests that the
absorbing and emitting states are the same (i.e., little electronic rearrangement occurs
between the absorbing and emitting states). As expected, the anisotropy value drops as
the excitation wavelength decreases, since the absorbing state is now a higher-energy
excited state than the emitting state. The excited complex must undergo internal
conversion in this situation to reach the emitting state, which would certainly change the
transition dipole and, consequently, the observed anisotropy.109 The anisotropies
recorded at the maximum of the structured emission shows a lower anisotropy value (0.1)

78
that does not vary across the excitation spectrum. This observation that the anisotropy is
nearly zero (i.e., the emission is almost completely unpolarized) and independent of
excitation wavelength is common when phosphorescence from a triplet excited state is
observed, since this state is typically very delocalized in the photoexcited
chromophore.109'111
300 350 400 450 500 550
Wavelength / nm
Figure 3-7: Excitation (dashed line) and excitation polarization (solid line) r(X) spectra at
80 K of 5-Re-3 2-MTHF solution at various emission wavelengths.

79
Based on the polarization data, the structured emission observed at low
temperatures is 37i,7i* phosphorescence originating from the complexed oligomer, while
the overlapping structureless emission that retains anisotropy is the MLCT emission after
undergoing an expected blue-shift from its room temperature position. Note, however,
that the phosphorescence anisotropy does not equal zero, indicating that some mixing of
phosphorescence and metal-based 3MLCT emission still occurs at low temperature.
Furthermore, the 3MLCT emission band wavelength is close to the 5-Re-l 80 K emission
maximum, further confirming its assignment. The presence of phosphorescence at lower
temperatures is likely due to nonradiative decay pathway restriction after the sample is
frozen in a glass. Similar overlapping MLCT and ligand emissions were reported by
Schmehl and coworkers in a rhenium complex with a styryl-substituted bipyridine ligand.
Low-temperature emission spectra of this complex exhibited overlapping metal-centered
and ligand-centered luminescence with differing lifetimes.112 The smaller oligomer
present in 5-Re-l evidently lacks the electron delocalization necessary to achieve the
“mixed-state” emission observed for the larger oligomers, since only 3MLCT emission is
observed.
One of the purposes for synthesizing the 5-ReAN complexes was to increase the
emission quantum yield and shift the MLCT emission away from the observed ligand
phosphorescence at low temperatures. Ligand substitution on (bpy)Re'(CO)3Cl to form
(bpy)Re’(CO)3(NCCH3)+ resulted in a 3MLCT emission maximum blue-shift of nearly
100 nm (from 642 to 540 nm), 3MLCT lifetime increase (from 150 to 1100 ns) and
emission quantum yield increase by two orders of magnitude (from 0.003 to 0.22).41,42
However, emission maxima of the 5-ReAN complexes are very similar to the

80
corresponding 5-Re molecules. The 80 K 3MLCT emission portion of the overlapping
spectrum is more prominent and slightly blue-shifted (around 575 nm) with respect to the
5-Re complexes, which might reflect the different chromophore excited state manifold
and potentially higher quantum yield relative to the in,n* phosphorescence resulting from
ligand substitution. Furthermore, room temperature quantum yield measurements on
5-ReAN-2 and 5-ReAN-3 remained very low (< 0.005), which is surprising. The
implications of these observations are presented below.
Emission Lifetimes
Emission decay lifetimes were recorded for the 5-L oligomers in 2-MTHF at
various temperatures and emission wavelengths. Both monoexponential and
biexponential decays were observed, and lifetime results are listed in Table 3-3.
Biexponential fits were performed using (3-3), yielding decay times (x¡) and normalized
amplitudes (a¡).
The room temperature lifetime of the oligomer 7t,7i* fluorescence generally
decreases with increasing oligomer size. On the blue side of the fluorescence band (450
nm), the fluorescence decay kinetics are single exponential at all temperatures (except
5-L-2). By contrast, on the low energy side of the fluorescence band (550 nm) the decays
become biexponential as the temperature decreases, featuring a long-lived component that
increases in amplitude with decreasing temperature. For 5-L-l, room temperature
biexponential decays are observed with little exhibited temperature dependence.
Although the amplitude of the long-lived component is small (< 0.04), the decay time is

81
significant, suggesting that at low temperatures this component substantially contributes
to the total emission yield.113 Note that the abrupt change in r(X) for both 5-L-3 (180 K)
and 5-L-4 (220 K) occurs at the same temperature where the emission decay kinetics
become biexponential.
Table 3-3: Variable temperature emission decay times of the 5-L oligomers.
Oligomer8
T/K
a,
450 nm Emission
Ti / ps a2
x2 / ps
a,
550 nm Emission
i! / ps a2
x2/ps
5-L-l
298
1
2215
-
-
0.986
2143
0.014
7935
80
1
1335
-
-
0.985
1384
0.015
8007
5-L-2
298
1
1124
-
-
1
1129
-
-
80
0.964
870
0.036
4067
0.954
0971
0.046
5093
5-L-3
298
1
952.2
-
-
1
1021.1
-
-
270
1
969.4
-
-
1
1059.3
-
-
230
1
1031.5
-
-
1
1218.5
-
-
200
1
979.3
-
-
1
1234.5
-
-
180
1
945.9
-
-
0.974
1535.8
0.026
8049.9
5-L-4
298
1
770.8
-
-
1
829.2
-
-
270
1
719.3
-
-
1
822.9
-
-
230
1
737.2
-
-
1
1054.0
-
-
220
1
493.6
-
-
0.992
1436.7
0.008
9287.5
210
1
434.3
-
-
0.991
1401.1
0.009
8785.6
190
1
458.3
-
-
0.992
1435.6
0.008
9350.0
“2-MTHF solutions; 350 or 405 nm excitation. Biexponential fits were performed with (3-3). Errors for the
fit parameters are ± 5%.
Emission decay lifetimes were recorded for the 5-Re complexes in 2-MTHF at
various temperatures, and lifetime results are listed in Table 3-4. At all temperatures, the
emission decays were biexponential and generally characterized by a large amplitude,
short-lived component (t « 1 ns, a > 0.95) and a low amplitude component with a

82
considerably longer lifetime (x « 20 - 200 ns, a < 0.05). The short-lived component
shows little temperature dependence, but the long-lived component increases from a few
hundred nanoseconds to several microseconds as temperature decreases. Note that the
short-lived component amplitude for 5-Re-2 - 5-Re-4 increases with increasing oligomer
size. Considering the fit error, the long-lived room temperature lifetimes (except 5-Re-l)
are equivalent.
Table 3-4: Variable temperature emission decay times of the 5-Re complexes.
Complex8
Temp. / K
«i
Ti / ns
a2
x2 / ns
5-Re-l
280
0.927
1.598
0.073
14.1
171
0.996
1.951
0.004
204
81
0.528
60.8
0.472
6237
5-Re-2
280
0.987
1.969
0.013
153.6
170
0.999
0.831
0.001
843.8
82
0.999
2.39
0.001
2489
5-Re-3
298
0.994
2.36
0.006
174
169
0.999
2.05
0.001
2430
82
0.999
5.12
0.001
5107
5-Re-4
298
0.991
3.834
0.009
170.5
80
0.999
7.753
0.001
7608
5-ReAN-2
298
0.998
0.182
0.002
8.506
170
0.995
0.389
0.005
6.363
80
0.993
0.362
0.007
5.733
5-ReAN-3
298
0.997
0.165
0.003
9.250
170
0.992
0.507
0.008
6.852
80
0.991
0.321
0.009
5.705
“2-MTHF solutions, 350 or 405 nm Excitation. Decays were recorded at 600 nm. Biexponential decay fits
were calculated based on (3-3).

83
Exhaustive studies of emission decays at various temperatures and emission
wavelengths were performed on all rhenium complexes, and representative data for
5-Re-2 are shown in Figure 3-8. Similar data sets were observed for the other rhenium
complexes. On the blue side of the emission (600 nm), the short-lived component
dominates the emission decay. The longer-lived component increases in amplitude as the
emission wavelength increases. For all wavelengths (as also seen in Table 3-4 for 600
nm), the longer-lived component amplitude decreases with decreasing temperature,
rendering the component relatively indistinguishable from the baseline at temperatures
less than 220 K. This data is further discussed below.
As described above, the low temperature emission for these complexes is believed
to be overlapping MLCT emission and oligomer 37i,7i* phosphorescence. Typically,
phosphorescence lifetimes are very long (tens to hundreds of microseconds). Clearly
these lifetimes were not observed in this data, which might indicate configurational
mixing of the two excited states. The increasing long-lifetime amplitude with increasing
emission wavelength suggests a greater contribution from the longer-lived oligomer 3n,n*
phosphorescence for these wavelengths, which agrees with the excitation polarization
data.
It is worth noting that the 5-ReAN complexes have short lifetimes for each of the
decay components that are temperature independent, unlike the other rhenium complexes.
Again, this is counter to the expected photophysical trends for acetonitrile-substituted
complexes as described above.

84
X¡
c
3
O
O
(A
c
V
(A
(A
E
LU
O 100 200 300 400
Decay Time / ns
Figure 3-8: Normalized emission decays (intensity versus time) of 5-Re-2 at various
emission wavelengths and temperatures. Emission decays increase in rate (i.e., more
rapid decay) with decreasing temperature, (a) 600 nm emission; (b) 650 nm emission;
(c) 700 nm emission.
Transient Absorption Spectra
Transient absorption spectra were recorded for all the oligomers and complexes,
and spectra for the 5-L oligomers are shown in Figure 3-9. Excited state lifetimes
obtained from factor analysis and global decay fitting'14 are listed in Table 3-1.
Equivalent first order decays were observed for all features of the various transient

85
absorption spectra. Bleaching of the long-axis n,n* ground state absorption (Figure 3-2)
was observed, along with a broad long-lived excited-state absorption extending into the
near-IR for all oligomers. However, 5-L-l shows a pronounced additional absorption at
500 nm. This absorption could be due to the lack of extended ^-conjugation in 5-L-l,
which could move excited states to higher energies and consequently blue-shift the
transition(s). Excited state lifetimes are very long (several hundred ps), which is typical
for organic triplets. Based on the lifetime, these transients are assigned to the 3n,7i*
excited state of the oligomers. The lack of a consistent trend in the TA lifetimes (Table
3-1) is a result of the extreme susceptibility of organic triplet excited states to oxygen
quenching, prompting the use of more rigorous freeze-pump-thaw degassing for these
compounds. The 5-L-3 and 5-L-4 transient absorption spectra also agree well with the
previously reported PI spectrum4^ and other n-conjugated polymers (Figures 1-2 and
1-8).
Transient absorption spectra for the 5-Re complexes in THF solutions are shown
in Figure 3-10. Spectra were recorded in CH2CI2 for the 5-ReAN complexes to prevent
CH3CN ligand photosubstitution. Excited state lifetimes obtained from factor analysis
and global decay fitting114 are listed in Table 3-2. Generally, equivalent first order decays
were observed for all features of the various transient absorption spectra. However, the
450 nm bleach transient sometimes exhibited biexponential decay with a rapid decay
component (x < 1 ns) followed by a longer-lived decay that agrees with the lifetimes of
the other transients. The lack of consistent biexponential behavior in all samples for this
decay suggests that trace 5-L fluorescence impurities were likely responsible for this
rapid decay component, since a similar rapid decay was evident in 5-L transient

86
absorption spectra when measured with a time resolution short enough to observe the
rapid signal.
Ground state 7i,7T* absorption bleaching similar to the free oligomer spectra was
observed at 450 nm, along with a strong absorption band around 500 nm and a broader
absorption band extending into the near-IR. The transient decay lifetimes are
significantly shorter than those for the free oligomers (10 - 200 ns). The similarity of the
bleach and 500 nm absorption to a derivative shape suggests that the lowest energy 71,71*
excited-state transition overlaps but is red-shifted with respect to the ground state, thus
producing the observed transient. The long-lived emission component and transient
absorption decay lifetimes are equivalent for all the 5-Re complexes except 5-ReAN-2
and 5-ReAN-3. This correspondence suggests that the transient absorption arises from
either the emitting excited state or an excited state that is in equilibrium with the
luminescent state. For 5-ReAN-2 and 5-ReAN-3, a considerably longer transient
absorption decay (several microseconds) was observed that is several orders of magnitude
longer that the emission lifetimes. The ramifications of the 5-ReAN observations are
discussed below.

87
a>
o
c
re
.o
k-
o
w
n
<
<3
0.04
0.03
0.02
0.01
0.00
-0.01
-0.02
-0.03
-0.04
0.010
0.005
0.000
-0.005
-0.010
-0.015
0.04
0.03
0.02
0.01
0.00
-0.01
-0.02
-0.03
0.015
0.010
0.005
0.000
-0.005
-0.010
-0.015
-0.020
400 500 600 700 800
Wavelength / nm
Figure 3-9: Transient absorption spectra of the 5-L oligomers in freeze-pump-thaw
degassed THF solutions. Arrows show the spectral trend with increasing time after laser
excitation. A value of zero indicates no change between the ground and excited state
absorption spectra. Transients are 40 ps increments after laser excitation, (a) 5-L-l;
(b) 5-L-2; (c) 5-L-3; (d) 5-L-4.

88
O
C
W
•D
O

n
<
<
400 500 600 700 400 500 600 700 800
Wavelength / nm
Figure 3-10: Transient absorption spectra of the 5-Re complexes in argon
bubble-degassed THF solutions (except for 5-ReAN-2 and 5-ReAN-3, which are in
CH2CI2). Arrows show the spectral trend with increasing time after laser excitation, (a)
5-Re-l (Transients are 4 ns increments after laser excitation); (b) 5-Re-2 (Transients are
80 ns increments after laser excitation); (c) 5-Re-3 (Transients are 80 ns increments after
laser excitation); (d) 5-Re-4 (Transients are 80 ns increments after laser excitation); (e)
5-ReAN-2 (Transients are 4000 ns increments after laser excitation); (f) 5-ReAN-3
(Transients are 4000 ns increments after laser excitation).

89
Photothermal Measurements
Using the TRTL apparatus described in chapter 2, the Usiow / Ujotai ratio of a
degassed THF solution of PI was determined to be 0.15. LIOAS measurements were
performed on THF solutions of the 5-L oligomers with the 1 MHz transducer and 5-Re
complexes with the 5 MHz transducer. For the 5-L oligomers, a single fast decay
component was observed, producing a single amplitude with an insignificant lifetime.
Results of multiple 5-L oligomer measurements are listed in Table 3-5. For the 5-Re
complexes, two components (fast and intermediate lifetimes) were observed.
Measurements on 5-Re-l were impractical due to its short excited-state lifetime, which is
below the xa value of our instrument. Results of multiple 5-Re complex measurements
are listed in Table 3-6. The triplet energies and yields of the 5-L oligomers are calculated
below. The triplet (3MLCT) energies of the 5-Re complexes can be calculated from each
of the two deconvolution amplitudes obtained from the LIOAS data in an analogous
manner to the (b)Re’(CO)3(bzpy)+ study described in chapter 2. Equations (2-15) and
(2-16) were used to determine the 3MLCT energies, and the results are listed in Table 3-7.
It was assumed that Oem * 0 and 0¡sc = 1 since the emission quantum yields are < 1 O'4.
Unfortunately, the measured triplet energies are radically lower than the observed
MLCT emission (anywhere from 686 to greater than 900 nm). The reason for this
discrepancy could stem from the assumption that the 3MLCT state yield is unity. Instead,
there could be a second excited state with a rapid nonradiative decay pathway that is
accessed to some degree upon photoexcitation. Alternatively, the presence of free
oligomer impurities could increase the radiated heat and lead to an erroneously low
energy calculation. Solvent electrostriction stemming from the large oligomers might

90
also cause incorrect photoacoustic measurements. Attempts at measuring LIOAS
transducer responses for 5-ReAN-2 and 5-ReAN-3 were unsuccessful due to possible
ligand dissociation and/or the presence of free oligomer.
Table 3-5: 5-L oligomer LIOAS data.
Oligomer3
.
5-L-l
0.2959 ±0.01
5-L-2
0.3021 ±0.04
5-L-3
0.3023 ± 0.02
5-L-4
0.2735 ± 0.02
aTHF Solutions, 298 K. LIOAS
deconvolution parameters are
averages of four measurements
on fresh sample solutions with a
reported error of ± a. Ti fixed at
10 ns.
Table 3-6: 5-Re complex LIOAS data.
Complex3
i
2
x2 / ns
5-Re-2
0.5150 ±0.032
0.4683 ± 0.036
122.2 ± 11.7
5-Re-3
0.5738 ± 0.022
0.3782 ± 0.074
152.7 ± 15.0
5-Re-4
0.5951 ±0.017
0.4383 ± 0.078
147.1 ± 14.7
aTHF Solutions, 298 K. LIOAS deconvolution parameters are averages
of four measurements on fresh sample solutions with a reported error of
± cr. Ti fixed at 1 ns.
Table 3-7: Triplet energies of the 5-Re complexes.
Complex3
ETb / kcal mol'1
Etc / kcal mol'1
5-Re-2
39.1 ±2.6
37.7 ±2.9
5-Re-3
34.3 ± 1.8
30.4 ± 6.0
5-Re-4
aTTxr o i . • „
32.6 ± 1.3
35.3 ±6.3
aTHF Solutions, 298 K. bTripIet energy based on the
first deconvolution amplitude and (2-15). ‘Triplet
energy based on the second deconvolution amplitude
with the assumptions that em = 0, lsc = 1 and (2-16).

91
Transient Absorption Quenching / Oligomer Triplet Energy
Triplet quenching rate constants (kq) for PI, 5-L-l, 5-L-3, and 5-L-4 were
obtained from Stem-Volmer analysis of the observed transient absorption triplet decay
lifetimes in freeze-pump-thaw degassed THF solutions as a function of quencher
concentration based on (3-4).
^- = l + kqT0[Q] (3-4)
X
In (3-4), to is the oligomer lifetime in the absence of quencher and x is the oligomer
lifetime observed with [Q] quencher concentration. A series of triplet acceptors of
varying energy41,97 were used as the excited state quenchers. All measured quenching
rate constants are listed in Table 3-8.
Table 3-8: 5-L oligomer and PI triplet quenching study results.
Quencher3
Ea/
kcal mol'1
kq/M'1
s'1
PI
5-L-l
5-L-3
5-L-4
Anthracene
42.5
1.2 x 1010
6.9 x 109
7.8 x 109
9.0 x 109
(deb)Re(CO)3Cl+
46.6
1.3 x 109
-
-
-
Pyrene
48.2
-
4.5 x 109
4.4 x 108
7.2 x 108
/rans-Stilbene
49.2
3.2 x 108
1.0 x 109
2.4 x 108
2.7 x 108
(bpy)Re(CO)3Cl+
52.0
3.7 x 107
-
-
-
9-Fluorenone
53.3
-
9.6 x 107
4.5 x 106
4.1 x 106
Biacetyl
56.4
1.5 x 105
3.6 x 105
9.5 x 104
9.9 x 104
/)-terphenyl
58.3
8.6 x 104
1.4 x 105
9.8 x 103
2.8 x 103
a(deb) - 4,4’-bis(carboethoxy)-2,2’-bipyridine; (bpy) = 2,2’-bipyridine. A correction factor of 5.7 kcal mol'1
was added to the rhenium complex EA values to correct for inaccurate Frank-Condon estimates.
Next, these quenching rate constants were used along with the photothermal data
to calculate the triplet 7t,7t* excited state energy. Unfortunately, due to the absence of

92
phosphorescence in most 7t-conj ugated polymers little is known about the absolute
energies and/or yields of triplets produced by direct excitation. In fact, to our knowledge
only one report from Bassler and coworkers115 on a rigid “ladder type” PPV polymer
reported Ti-conjugated polymer phosphorescence. However, there are indirect methods
with which the triplet energy and yield can be determined. Here, the oligomer triplet
energies are calculated by fitting experimental Sandros plots116 (log kq vs. EAcCeptor) with
(3-5), a Marcus equation that is appropriate for bimolecular reactions that occur at or near
diffusion control.117,118 This same method was used to calculate the triplet energy for
MEH-PPV as mentioned in chapter 1,22
ÍAG]
fkdl
1 + exp j +
[RT j
k°
(Ken J
expjAG )
(3-5a)
A , f, f-AGln2N
AG = AG + In j 1 + exp
In 2
(3-5b)
In (3-5), kd and k_d are the rate constants for forward and reverse diffusion in solution, ken0
is a preexponential factor, X is the reorganizational energy and AG = (E°°Acceptor - Ej). By
using parameters derived from a previous report of rhenium complex quenching studies91
(kd = 1.0 x 1010 M'1 s'1, k.d = 2.0 x 1010 M'1 s'1, k^0 = 5 x 1010 s'1), best fits of the Sandros
plots for PI and the 5-L oligomers are obtained by varying X, and ET in (3-5). These
values are listed in Table 3-9, and plots of the fitted quenching data are shown in Figure
3-11.
The photothermal data obtained for PI and the 5-L oligomers can now be used in
conjunction with the calculated triplet energy to determine the triplet yield, which is

93
derived from the PI TRTL data and the 5-L LIO AS single component deconvolution
with (3-6) and (3-7), respectively. Calculated triplet yields for PI and the 5-L oligomers
are listed in Table 3-9.
Usiow _ EtQt
U Total
(3-6)
Ehu Es®em -EtQt
Ehü
(3-7)
The triplet yields increase from 5-L-l - 5-L-3 followed by an observed decrease
in 5-L-4. Furthermore, the sum of the fluorescence (Table 3-1) and triplet yields is close
to unity (0.939 to 0.959), which indicates that photoexcitation of the oligomers leads
almost exclusively to radiative decay or intersystem crossing (i.e., very little nonradiative
decay occurs from the singlet state). The singlet-triplet splitting energy (Est = Es - Et) is
also listed in Table 3-9 and shows a steady increase as the oligomer length increases, with
the largest reported splitting found in the PI polymer.
Decay Rate Calculations
Sufficient data is now available to calculate the radiative (kr), intersystem crossing
(kisc), and nonradiative (knr) decay rate constants for the 5-L oligomers based on (3-8).
^ em
(3-8a)
(3-8b)
1 ^ em (k r ^ isc )
(3-8c)

94
The spectral data can also be used to calculate kr with the Strickler-Berg equation,
(3-9).119
= 2.88x10-9r|2 (vF3\
r(v)dv
(3-9a)
\ /AV 1
J V
\ fl(vF)dvF
AV" Jvp3l(vF)dVF
(3-9b)
In (3-9), r\ is the solvent refractive index (THF, 1.4070), e(v) is the molar absorptivity of
the absorption spectrum (M'1 cm’1), v is the absorbance wavenumber (cm’1), l(vF )is the
intensity of the normalized fluorescence spectrum, and vF is the fluorescence
wavenumber (cm1). For these calculations, only the lowest-energy absorption band was
integrated. The experimental and calculation results are listed in Table 3-10.
Many observations are suggested from this data. First, note that kr increases as the
oligomer size increases. This trend is not surprising considering the delocalization
increase provided by the oligomer size increase. Second, the calculated krSB values agree
well with the experimentally-determined rates within a factor of two. This agreement
confirms that the fluorescence originates from the same state that gives rise to the
lowest-energy absorption band. In addition, the fact that the radiative decay rates are
relatively large and close to those calculated with the Strickler-Berg equation indicates
that the fluorescence arises from a strongly allowed radiative transition.29 Third, knr and
k,sc exhibit the same increase with oligomer size, but to a much lesser extent. The relative
steadiness in knr from 5-L-2 - 5-L-4 shows that the increased oligomer conjugation does
not extensively alter the excited state manifold energy levels.

95
Figure 3-11: Sandros energy-transfer quenching plots (log (kq) versus acceptor energy).
Points are experimentally determined rate constants with various triplet energy acceptors
(1. anthracene, 2. [4,4’-bis(carboethoxy)-2,2’-bipyridyl]Re(CO)3Cl, 3. pyrene, 4. trans-
stilbene, 5. (2,2’-bipyridyl)Re(CO)3Cl, 6. 9-fluorenone, 7. biacetyl, 8./?-terphenyl), and
fitted lines are calculated based on (3-5). (a) PI; (b) 5-L-l; (c) 5-L-3; (d) 5-L-4.

96
Table 3-9: Triplet photophysics of PI and 5-L oligomers.
Compound3
Es / cm'1
(kcal mol1)
X/cm'1 Ej/cm'1
(kcal mol'1) (kcal mol'1)
Oy
Est / cm 1
PI
23,100 (66.0)
1200(3.43) 17,500(51.2)
0.12
5,600
5-L-l
22,000 (62.9)
1050(3.00) 18,300(52.3)
0.049
3,700
5-L-2
22,030(63.0)
17,700 (50.6)b
0.214b
4,330
5-L-3
22,080 (63.1)
1200(3.43) 17,700(50.6)
0.262
4,380
5-L-4
22,120 (63.3)
1100(3.14) 17,500(50.0)
0.169
4,620
“Errors for the triplet yield are ± 15%. bValues for 5-L-2 are estimated from 5-L-3 values.
Table 3-10: Decay rates of the 5-L oligomers.
Oligomer
kr/10V
Kr /107 s'1 k¡sc /108
s'1
krSB /108 s'1
5-L-l
4.02
2.75 0.221
6.48
5-L-2
6.41
5.87 1.90
8.66
5-L-3
7.14
6.09 2.75
11.6
5-L-4
10.2
5.32 2.19
22.6
PI
11.0
5.70 2.30
-
Excited-State Energy Transfer
Emission studies were conducted on mixtures of various 5-L oligomers and 5-Re
complexes with the intent of observing energy transfer between the oligomer (donor) and
rhenium complex (acceptor). A representative variable temperature study of a 1:1
mixture of 5-L-3 and 5-Re-3 in 2-MTHF is shown in Figure 3-12. As the sample
temperature decreased, the 5-L-3 n,n* fluorescence decreased and the 5-Re-3 MLCT
luminescence increased. Recall that the oligomer fluorescence quantum yield is at least
j|( • » • • • •
The initial emission intensity increase seen in Figure 3-1 lb was due to the 5-L-3 7t,7t*
fluorescence red-shift.

97
three orders of magnitude greater than the complex luminescence, which explains the
very weak 5-Re-3 emission. The observed behavior is not surprising, as each individual
component mirrors their temperature responses reported above (Figures 3-3 and 3-5).
What appears different in the mixed sample is the complete loss of oligomer fluorescence
between 190 and 170 K, which is close to the freezing point of 2-MTHF. Table 3-11 lists
ratios of the oligomer n,n* fluorescence at room and low temperatures both by itself and
mixed with rhenium complexes in varying proportions.
Wavelength / nm
Figure 3-12: Emission spectra of a 1:1 mixture of 5-L-3 and 5-Re-3 (2 x 10'6 M) in 2-
MTHF at various temperatures ranging from 298 to 80 K in 20 K increments. Arrows
show the spectral trend with decreasing temperature. Note the sharp drop in n,n*
fluorescence at 170 K, signifying energy transfer, (a) 5-L-3 n,n* fluorescence (350 nm
excitation); (b) 5-Re-3 MLCT luminescence (450 nm excitation).

98
Table 3-11: Fluorescence intensity ratios for mixed samples.
Sample3
I298K/
/^SOK
129Sk/ (rei)
/^OK
5-L-3
7.14
1.00
1:1 5-L-3:5-Re-3
96.69
13.54
1:2 5-L-3:5-Re-3
128.8
18.04
2:1 5-L-3:5-Re-3
185.4
25.97
1:1 Pl:5-Re-3
34.53
4.84
5-L-4
8.69
1.22
1:1 5-L-4:5-Re-4
31.90
4.47
“Measurements were conducted on optically dilute 2-MTHF solutions (2 x 10'6 M). Emission intensities
used for the ratios are the fluorescence band maxima at 298 and 80 K.
Oligomer fluorescence quenching markedly increased with the addition of the
rhenium complexes, indicating energy transfer between the two excited states. Note that
efficient energy transfer occurred even with a 2:1 ratio of oligomer to complex. The
increased ratio observed for the 2:1 5-L-3:5-Re-3 sample, which is counter to the
expected trend, is due to the larger initial oligomer emission while the low temperature
intensity for all the 5-L-3:5-Re-3 samples is essentially equivalent to the baseline noise as
seen in the Figure 3-17a inset. This indication of energy transfer in fluid solutions
prompted further investigation into solid-state energy transfer.
Langmuir-Blodgett Films
The Langmuir-Blodgett (LB) film process has been utilized for several years to
produce multi-layer films of complex molecular systems with the purpose of studying
their material properties.120 This process has been used to create films of rigid-rod
polymers similar in structure to the 5-L oligomers.51,121'123 Therefore, it was theorized

99
that the energy transfer observed in solution could also be observed in LB films where the
donor (5-L oligomer) and acceptor (5-Re complex) could be mixed in the same layer or
deposited in alternating layers. A collaboration with Dr. Dan Talham and postdoctoral
associate Dr. Aiping Wu at the University of Florida was initiated to explore this theory.
LB films consisting of a single component were initially transferred to compare
with the solution photophysics. A -Ru(bpy)22+ analogue of 5-Re-2, 5-Ru-2,100 was used
because of its higher luminescence quantum yield, allowing for easier detection in the
presence of the highly fluorescent free oligomer. A spread layer of 5-Ru-2 exhibited a
good compression isotherm, indicating that a reasonable monolayer was formed on the
LB trough surface. Films of varying layer thicknesses were transferred onto glass
substrates and their photophysics studied. Transfer ratios of these films were close to
unity for both the up and down transfer strokes. Absorption and emission spectra of the
5-Ru-2 films along with solution spectra are shown in Figure 3-13.
The 5-Ru-2 LB film absorption spectra feature two n,n* absorptions similar to
those observed in the solution spectra. Only a slight red-shift is observed between the
solution and LB film maxima.124 Except for the thickest film, the lowest-energy
absorption maximum exhibits a linear dependence on film thickness (0.0038 a.u. layer'1)
as seen in the Figure 3-13b inset. Using this trend, the LB film surface coverage can be
calculated using (3-10), a modified Lambert-Beer equation.
A = eTL (3-10)
In (3-10), T is the surface coverage (mol cm'2 layer'1) and L is the number of layers within
the film. If it is assumed that the molar absorptivity of the band maximum in solution
and the LB film is equivalent (5.31 x 107 cm2 mol'1), using the calculated absorption

100
increase above a surface coverage of 7.16 x 10’11 mol cm’2 layer’1 is determined. The
inverse of this value after unit conversion produces the mean molecular area (MMA) of a
single 5-Ru-2 molecule, 231.9 Á2 molecule'1. Another method of determining MMA, the
construction of a line tangent to the pressure isotherm of the 5-Ru-2 monolayer, gives a
MMA essentially equivalent to the value determined by absorption spectroscopy (208 Á2
molecule’1).
The 5-Ru-2 LB film emission spectra exhibit a fairly weak 3MLCT luminescence
that is slightly red-shifted from solution 5-Ru-2 spectra.124 Unlike the absorption spectra,
no decisive trend is observed between emission intensity and film thickness. There could
be many reasons for this observation, including LB film heterogeneity and/or self¬
quenching. However, emission intensity varied only by ±10% when different areas of the
sample were probed, and preliminary fluorescence microscopy studies indicated that the
LB films were homogeneous. Note that polarized absorption and emission measurements
on these films failed to indicate any preferential anisotropy, which was observed for PPE-
type polymer LB films.51125 The absence of polarization in these films is likely due to the
formation of mesoscale-sized domains that would exhibit polarization on a microscopic
measurement but cancel each other out in the macroscopic measurements presented here.

101
300 350 400 450 500 550 600
500 550 600 650 700 750 800 850
c
£
re
J-
+-»
n
u.
<
in
c
a>
c
c
o
'«
in
E
LU
1 Layer (1)
2 Layers (2)
4 Layers (3)
6 Layers (4)
12 Layers (5)
24 Layers (6)
Wavelength / nm
Figure 3-13: Photophysics of 5-Ru-2 Langmuir-Blodgett films, (a) 5-Ru-2 THF solution
absorption (solid line) and emission (dashed line) spectra; (b) Absorption spectra (inset:
absorbance maximum vs. number of layers); (b) Emission spectra (450 nm excitation;
inset: emission maximum vs. number of layers).

102
Several attempts were also made to transfer LB films of 5-L-3, but the lack of
charge on the oligomer presented a large handicap. Pressure isotherms of the oligomer
indicate a very small MMA (50 Á2, see Figure 3-14), and aggregation was visibly
observed on the trough surface. Films were not transferrable from these rigid aggregates.
Several different “tricks” were utilized to overcome the aggregation problem and/or
induce charge on the oligomer, including protonation of the bipyridyl nitrogens at low
pH, addition of a surfactant (didodecyldimethylammonium bromide), and the formation
of oligomer complexes with other metal cations (Cu2+, Ni2+ and Mn2+). In all cases,
transferred LB films were visually heterogeneous and exhibited grossly broadened
fluorescence, suggesting aggregation.
A series of five-layer LB films were transferred with varying ratios of the 5-L-3
oligomer and 5-Ru-2 complex which are pre-mixed prior to spreading. Transfer ratios of
these films are again close to unity for both up and down transfer strokes. Pressure-area
isotherms of the mixed 5-L-3 / 5-Ru-2 films are shown in Figure 3-14. Reported ratios
are the molar ratios of the premixed solution that is spread on the LB trough.
All the mixed LB film pressure isotherms are reasonably well behaved. Note that
the MMA increases with increasing amounts of 5-Ru-2, which is reasonable since the
ruthenium complex has a larger molecular area than the free oligomer. Absorption,
emission, and excitation spectra of the mixed LB films are shown in Figure 3-15.
Absorption spectra of the mixed LB films exhibited two 7i,Tt* absorptions and a low-
energy tail which is assigned to an MLCT-based absorption. Absorbance decreases with
increasing 5-Ru-2 concentration, which is expected since the free oligomer has a higher
absorptivity. A 15 nm red-shift in the lowest-energy n,n* absorption was also observed

103
with increasing 5-Ru-2 concentration. It is interesting to note that the MLCT “shoulder”
does not dramatically change in intensity between the various films, but the relative
intensity of the n,n* compared to MLCT absorptions decreases with increasing 5-Ru-2
concentration. Using (3-10) and solution molar absorptivity values, MM A values were
calculated based upon the low-energy n,n* absorption maximum. A comparison of
MMA values calculated spectroscopically and from the pressure isotherms is presented in
Table 3-12. The calculated MMA values are lower than the pressure isotherm data.
These differences are likely due to errors introduced by assuming the calculated solution
absorptivities are valid for LB film measurements or the existence of an extended
interaction between donor and acceptor molecules in the mixed LB films.
Figure 3-14: Pressure isotherms of Langmuir-Blodgett films of 5-L-3 / 5-Ru-2 mixtures.
Ratios are [5-L-3] : [5-Ru-2] in the premixed solution prior to spreading.

104
Table 3-12: Surface coverage calculations for mixed 5-L-3 / 5-Ru-2 LB films.
[5-L-3] : [5-Ru-2]
MMA" / Á2
T / 10'10 mole cm'2 layer'1
MMAb / Á2
2: 1
123
1.69
98.8
1 : 1
150
1.52
109
1 :2
180
1.28
130
1 :4
205
1.26
132
aMMA calculated from
pressure isotherms. bMMA
calculated from absorption spectra.
Emission spectra show 5-Ru-2 MLCT luminescence that is very similar to the
emission observed in the single-component LB film (Figure 3-13). The relative intensity
of the 5-L-3 n,n* fluorescence (the peak extending to lower wavelengths in Figure 3-15b)
decreases with increasing 5-Ru-2 concentration, which is not surprising. However,
examination of the excitation spectra shows that excitation wavelengths producing the
MLCT luminescence blue-shift with increasing 5-L-3 concentration. This trend indicates
that energy transfer is occurring between the two components, since excitation into the
oligomer n,n* absorption clearly produces 3MLCT emission.
Unfortunately, there were problems with the mixed LB film experiments. Note
that the emission and excitation spectra in Figure 3-15 are normalized. The absolute
MLCT emission intensities for these films varied wildly, with the highest concentration
5-L-3 film exhibiting MLCT emission five times more intense than any of the other
films. Again, heterogeneity within these mixed films could be responsible for these
photophysical observations, and fluorescence microscopy appeared to indicate some
striation within the LB films that may be due to mesoscale-range phase segregation.
Furthermore, the inability to transfer single-component 5-L-3 LB films prevents the full
understanding of the mixed film photophysics.

105
r5-L-31 : fS-Ru-21
2:1
1:1
1:2
1:4
Wavelength / nm
Figure 3-15: Photophysics of 5-L-3 / 5-Ru-2 mixed Langmuir-Blodgett films, (a)
Absorption spectra; (b) MLCT Emission spectra (409 nm excitation); (c) MLCT
Excitation spectra (694 nm emission).

106
Electrochemistry
Cyclic voltammetry was performed on the 5-Re complexes in THF with 0.1 M
tetrabutylammonium hexafluorophosphate (TBAH) as supporting electrolyte.
Unfortunately, the complexes were not soluble in more polar solvents typically used for
electrochemistry, and measurements on CH2CI2 solutions produced poor results. Due to
the limited potential window of THF (anodic limit » +1.4 V), oxidation potentials could
not be measured. However, quasi-reversible reduction waves of the ligated oligomer
were observed in all cases except 5-Re-4, which had a non-reversible reduction.
Reduction half-wave potentials are listed in Table 3-2. Note that the reduction potential
does not dramatically shift with increasing oligomer size. The reduction potentials are
less than the parent complex (bpy)Re(CO)3Cl (-1.35 V vs. SCE),41 which indicates that
the 5,5’-substituted aryl-ethynyl moieties on the bipyridine stabilize the reduced complex
(i.e., the LUMO energy is lowered by the 71-conjugation). This observation further
implies that in the reduced complex there is some electron density delocalization in the
appended aryl-ethynyl units. Reduction half-wave potentials were also measured for 5-L-
3 and 5-L-4 under similar conditions. For both oligomers, values of-1.46 V vs. SCE
were obtained. Therefore, complexation of the oligomer to the metal center makes it
easier to reduce the oligomer by nearly 0.5 V.
Discussion
Oligomer Ligand Conformation
Many spectroscopic observations reported above can be better understood when
the effective conjugation length due to oligomer conformation is considered. The extent

107
of oligomer conjugation is dominated by “breaks” caused by twists in the bipyridine and
biphenyl subunits of the oligomer backbone. These twists are induced by steric effects
due to the close proximity of a-hydrogens on adjacent phenyl rings. Wasielewski and
coworkers discussed this same phenomenon with a 2,2’-bipyridyl-conatining BEH-PPV
(Figure 1-1 ),24 where the excited-state energy via absorption spectroscopy is higher for
the polymer with the 2,2’-bipyridine subunit due to these conjugation breaks. Two major
conclusions lead from this structural observation: 1) An oligomer size increase may not
bring a corresponding conjugation length increase; and 2) Rhenium complexation leads to
a marked oligomer conjugation increase. For example, when the oligomer length is
increased from 5-L-l to 5-L-2, a conjugation increase is expected because the majority of
each side of the oligomer is expected to be planar. However, further lengthening to
oligomers 5-L-3 and 5-L-4 introduce opportunities for the conjugation to be broken at the
biphenyl subunits. Therefore, the resulting conjugation increase may not be as large as
anticipated. Furthermore, the long alkyl chains on the dialkoxybenzene subunits present
for solubility provide a driving force for varied conformations that may be entropic in
nature.
When the oligomers are ligated to a rhenium chromophore, as seen in Figure 3-16,
the metal center forces the typically orthogonal bipyridine subunit into a planar
conformation. This conformation facilitates a significant conjugation increase when
compared to the uncomplexed oligomer. However, peripheral biphenyl subunits are
likely still twisted as illustrated. Recall that the consequences of metal complexation was
utilized by Wang and Wasielewski18 to create metal ion sensors with their 2,2’-
bipyridine-substituted PPV polymers (Figure 1-9). Metal ion complexation to these

108
polymers induced absorption and fluorescence red-shifts of up to 100 nm in certain cases.
With these two effects in mind, the photophysical observations can be interpreted with a
greater understanding of the connection between oligomer structure and photophysical
properties.
M
OR
OR
Figure 3-16: Effect of metal complexation to the conjugated segments of the oligomer.
Electronic absorption spectra
For the 5-L oligomers, recall that following an initial red-shift from 5-L-l to
5-L-2, the lower-energy n,n* transition remained at a constant wavelength for oligomers
5-L-2 - 5-L-4, suggesting that the oligomer bandgap (405 nm = 3.06 eV) had been
reached. The biphenyl conjugation breaks do not allow further delocalization and,
consequently, additional red-shifting. Flowever, the increased overall size of the oligomer
still increases the electronic transition dipole, which in turn increases the oscillation
strength of both n,n* transitions, resulting in the observed intensity increase. The PI

109
absorption spectrum mirrors the oligomer absorption band maxima, suggesting that these
same conjugation limitations exist in the polymer.
For the 5-Re complexes, following an initial increase and red-shift from 5-Re-l to
5-Re-2, the oscillator strength and wavelength of the lower energy 71,71* transition band
remains relatively constant as the oligomer size increases. The red-shifted 7t,7t* transition
with respect to the free oligomer is due to the forced oligomer bipyridine planarity and the
resulting conjugation increase (Figure 3-16), in addition to potential contributions from a
charge transfer band. Recall, however, that the absorptivities are exceedingly high for a
solely MLCT-based absorption. Similar red-shifts are seen in the 5-ReAN complexes.
The central chromophore is electronically isolated from the remainder of the oligomer
due to biphenyl conjugation breaks, which leads to the observations of “constant” and
“varying” portions of the absorption spectrum as described above. Since the outer
sections of the oligomers do not experience any significant conjugation effect upon
rhenium complexation, it continues to electronically behave as the free oligomer would.
Therefore, we observe the evolution of bands that represent different segregated
chromophores on the same oligomer chain. For example, 5-Re-4 is large enough to
effectively isolate “all-organic” chromophores from the central section so that the
absorption spectrum exhibits both the same two electronic transitions seen in unbound
oligomer 5-L-4 (343 and 388 nm) along with the red-shifted 71,71* absorption seen in
rhenium complexes 5-Re-l - 5-Re-3 (444 nm).
Emission spectra
As seen above, the fluorescence quantum yields decrease and triplet yields
increase as oligomer size increases, which is due to greater electron delocalization in the

110
larger oligomers. However, the lack of significant yield variation between 5-L-2 and
5-L-3 further suggests no significant delocalization increase due to the oligomer
backbone conjugation breaks. The fluorescence yield increase observed for 5-L-4 could
result from concurrent emission from an electronically isolated second chromophore in
the same oligomer.
The increasing spectral complexity (i.e., “blurring” of the spectra) of the 5-Re
complexes (except 5-Re-l) may also have its roots in the oligomer conformation. As the
complexes are confined in the solvent glass, the biphenyl units can potentially be trapped
in a wide variety of rotational conformations. These various conformations lead to an
effective conjugation length distribution and, consequently, multiple 37t,7i* energy levels
in the sample. This distribution would lead to an overall emission band broadening
similar to the experimentally observed spectra.
Oligomer triplet energies
The photophysical characterization of the triplet excited state of PI and the 5-L
oligomers allows us to assess the effect that extended ^-conjugation has on its properties.
It is surprising that Ej (i.e., triplet energy) is the same for the 5-L oligomers within error,
but the ESt value (Table 3-9) increases slightly (< 2 kcal mol'1) as the oligomer length
increases. Logic suggests that the splitting energy would decrease as the oligomer size
increases as a consequence of decreased electron exchange energy, which presumably is
due to the fact that the n —> n* transition delocalization is greater as the extended 71-
conjugation increases.126 In fact, an inverse relation between Est and oligomer size is
observed by Becker and coworkers for a series of oligothiophenes.30 The biphenyl twists
in our oligomers break the potential conjugation and limit the delocalization impact on

Ill
the excited-state energies, resulting in similar Ej values across the series. These same
conjugation breaks in the polymer result in the similar oligomer and PI triplet energies.
The oligomer and polymer singlet excited state energy difference is due to the presence of
the bipyridyl subunit in the oligomers. In fact, Est is almost 1000 cm'1 lower in PI (5600
cm1) compared to a biphenyl analogue of 5-L-l (6500 cm'1). The triplet energies for
these oligomers and polymer are significantly higher than the PPV and polythiophene
triplet energies previously reported (29 - 35 kcal mol'1), which is likely a direct result of
the conjugation limitations imposed by the bipyridine and biphenyl subunits.
Oligomer Temperature Dependence and Aggregation
It has already been seen that in dilute solution alkyl- and alkoxy-substituted PPV,
PPE and related polymers and oligomers feature strong absorption and fluorescence
bands arising from long-axis 7i,7r* transitions on a single polymer chain (i.e., intrachain
excitations). In contrast, the solid state photophysics of the polymers (i.e., as amorphous
films) originate from states that absorb and luminesce at a lower energy than the solution
intrachain n,n* bands. ’ ’ Although it is clear that the photophysical properties of the
polymers in the solid state arise from “excimer-like” states created by interchain
interactions, little evidence was available until recently for the involvement of interchain
states in dilute solution polymer photophysics.129'134 Aggregation examples include a
cyano-substituted alkoxy-PPV polymer (both in solution and in the solid state), where
aggregation was attributed to competition between luminescence from intrachain and
interchain (excimer) states arising from chromophore aggregates.129'131 Additionally, it is
known that poly-3-alkylthiophenes exhibit thermochromism and solvatochromism that is
due in part to aggregation.132'134 Several of the oligomers presented here exhibit these

112
same characteristics, which suggest that the oligomers aggregate in dilute solution at low
temperatures. However, aggregate formation has not been previously reported for dilute
n-conjugated oligomer solutions such as the 5-L oligomers.
The temperature dependence of the 5-L oligomer emission (Figure 3-3) illustrates
that the 7r,7i* fluorescence observed from dilute solution red-shifts, broadens and
decreases in intensity with decreasing temperature. The fluorescence is dominated by a
broad red-shifted band, a feature typically associated with “excimer” emission from an
excited state dimer. These effects are opposite to what is typically observed for aromatic
fluorophores, where lowering the temperature usually induces a blue-shift with a
corresponding fluorescence lifetime and quantum yield increase because knr decreases
with decreasing temperature.113 The decay rate is proportional to the excited-state /
ground-state vibrational overlap, which decreases with temperature due to a decrease in
the Boltzmann excited vibronic level population and decreased electron-phonon coupling
to outer-sphere solvent modes. Indeed, for the lowest temperature emission spectra in
5-L-l the typical trend described here is observed, but only after the “sample
aggregation” is apparently complete. The larger oligomer spectra do not exhibit this same
blue-shift, apparently because an energy deactivation pathway more favorable than
fluorescence is available to the oligomer excited state.
The oligomer temperature-dependent fluorescence data strongly suggests that the
oligomers exist in an aggregated state in low temperature solution. Furthermore, the
broad, red-shifted fluorescence band features a longer decay time (several ns) than the
blue "monomer" emission (< 1 ns). This longer decay time is also consistent with an
aggregated or “excimer-like” state, since an excimer state would have a lower kr (and

113
consequently a longer decay time) compared to a monomer excited state. This rate
decrease is due to the fact that the exciplex radiative decay rate is proportional to the
square of the ground state monomer to excited state exciplex transition moment. If the
exciplex exhibits charge transfer behavior (as indicated below), the transition moment
decreases from its monomeric level, leading to the observed kr decrease.135
The key to confirming aggregation as the probable mechanism for the
fluorescence temperature-dependence lies in the 5-L-3 and 5-L-4 polarization anisotropy
data. Under ordinary conditions, the polarization anisotropy of a fluorophore in dilute
solution increases with decreasing temperature.109 The increase occurs because the
primary mechanism for polarization loss in dilute solutions is rotational diffusion, which
slows with increasing solvent viscosity. An alternate depolarization mechanism is long-
range (Forster) energy transfer or exchange energy migration among aggregated
chromophores. Thus, under conditions where rotational diffusion is slow (i.e., at
cryogenic temperatures), observation of depolarization is a strong indication that energy
transfer migration within chromophore aggregates occurs.
With these facts in mind, the temperature-dependent anisotropy data for 5-L-3 and
5-L-4 is examined. For 5-L-3, as temperature decreases the anisotropy slightly increases
as expected due to the rotational diffusion rate decrease (Figure 3-5). However, below
190 K there is an abrupt anisotropy decrease, suggesting that at this temperature
aggregation occurs. For 5-L-4, the anisotropy also increases slightly with decreasing
temperature then drops precipitously between 230 and 210 K, which is also due to
chromophore aggregation. Note that the anisotropy data implies that 5-L-4 aggregates at
a higher temperature than 5-L-3, consistent with the fact that 5-L-4 is a larger “rod” than

114
5-L-3 based on semi-empirical calculations (5-L-3: length = 59.1 Á, four n-CisH37 alkyl
side-chains; 5-L-4: length = 95.3 Á, eight n-Cig!-^ alkyl chains).
Although it is clear that the oligomers aggregate at low temperature, two subtle
features demand a more complicated model for explanation: 1) At intermediate
temperatures (i.e., 298 > T > 220 K) the fluorescence is dominated by emission from the
“monomeric” excited state, but the band steadily red-shifts and decreases in intensity with
decreasing temperature; 2) An abrupt change in the fluorescence bandshape, decay
kinetics and wavelength-dependent polarization anisotropy occurs at T w 220 K for 5-L-4
and T w 180 K for 5-L-3. This latter feature implies that a dramatic change occurs in the
system properties that arise from intermolecular aggregation.
Because the polarization anisotropy remains high at intermediate temperatures
(i.e., 298 > T > 190 K for 5-L-3 and 298 > T > 230 K for 5-L-4), energy transfer resulting
from aggregation must not occur at these temperatures. Therefore, these spectral changes
must arise from intramolecular effects. We conclude that these effects arise from
variations in the oligomer backbone and side chain conformation. As temperature
decreases, the oligomers may adopt conformations in which the phenylene rings for the
oligomer series lie more within the same plane. A ^-conjugated system planarity increase
would effectively increase the conjugation length, which in turn decreases the ‘71,71*
transition energy that is responsible for the red-shifting fluorescence. This energy
decrease may also increase knr, resulting in the observed fluorescence yield (i.e., intensity)
decrease.136
An important consideration in formulating this mechanism is that the oligomer
backbone and n-CisH37 alkyl side chain conformations must be correlated. Indeed, as the

115
oligomer n-system becomes more planar, the n-Cig^ alkyl side chains probably tend to
lie essentially in the same plane. It is possible that as temperature decreases the
oligomers and side chains may adopt a planar “sheet-like” conformation that is the
precursor to the formation of extended aggregates as suggested in Figure 3-17.
Cooperation between side chain conformation and intermolecular interactions has been
proposed to occur in “hairy-rod” Ti-conjugated polymers similar in structure to the
oligomers,133 but this study may be the first example of such an effect in medium
molecular weight “hairy-rod” oligomers.
Ambient Temperature
~—-X
Intermediate Temperature Low Temperature
(Conformation Effect) (Aggregation Effect)
Figure 3-17: Proposed oligomer aggregation mechanism.
Excited State Photophysics of the Rhenium Complexes
Initially, it was believed that the same excited state (the 3MLCT state) was
responsible for both the observed emission and transient absorption spectra. However,
two pieces of data could not be explained by this theory: 1) The emission decay is never
single exponential, displaying a predominant rapid decay component before the assigned
MLCT decay; and 2) The different emission and transient absorption lifetimes of the
5-ReAN complexes show that the same excited state cannot be responsible for both
spectral results. Therefore, a new excited-state model is derived that takes these

116
observations into account and is illustrated in a Jablonski diagram in Figure 3-18. This
model is based on the existence of an equilibrium between two excited states, 3n,7t*
(oligomer-based phosphorescence) and 3MLCT (metal-based luminescence). The
3MLCT state is responsible for the observed emission (EM in Figure 3-18), while the
"3 #
71,71* state is responsible for the excited-state absorption observed in the transient
absorption spectrum (TA in Figure 3-18).
Using this model, the unusual photophysics observed in the emission lifetime
decays and disparate 5-ReAN excited-state observations can now be explained. First, the
biexponential decay observed in the emission data is the result of an equilibrium that is

117
rapidly established between the two excited states following initial photoexcitation. The
large-amplitude rapid component represents 3MLCT emission which quickly decays to
the 37i,7i* state that is non-emissive at room temperature. The slower decay component is
the remaining emission after equilibration, which is either 3MLCT at room temperature or
a mixture of both MLCT and 7i,7t* at low temperature.
Following equilibration, the population remaining in the 7i,7i* state is available to
be excited into a higher triplet excited state, producing the obtained transient absoption
spectrum. In principle, the 3MLCT transient absorption should be seen at early delay
times following laser excitation, but our instrument does not have the capability to
resolve such fast decays. Preliminary investigations on a picosecond time-resolved flash
photolysis system in collaboration with Professor Mike Wasielewski at Northwestern
University, however, did show some spectral evolution on the timescale of the excited-
state equilibrium process. ’ ’ The broad observed absorption seen in all the 5-Re
spectra (Figure 3-9) mirrors the 5-L oligomers spectra well, further supporting this
assignment. The sharp 500 nm band is believed to be a derivative remnant of the
overlapping ground and excited-state absorbances at that wavelength rather than a unique
excited-state absorption. The excited state equilibria result in identical decay rates of
both states following equilibration, which is a common result for this equilibria.139'141
The 5-ReAN complexes, however, do not have equivalent emission and transient
absorption decay rates. Upon replacing the chloride ligand with an acetonitrile, the
MLCT excited state is raised in energy due to n backbonding with the acetonitrile ligand,
which draws electron density away from the metal center and increases the ligand field
splitting.142 Consequently, the excited state equilibrium is disrupted, leading to a rapid

118
i
MLCT emission decay as it undergoes internal conversion to the 7t,7t* state with no
•3 3
opportunity for reverse conversion to MLCT as seen in the 5-Re complexes. This
state can then undergo triplet-triplet absorption and exhibit a longer decay time that is
more typical of organic triplet absorptions.
To further confirm that the transient absorption originates from the 37i,7i* excited
state, time-resolved continuous-wave EPR (TREPR) studies were performed in a
collaborative effort with Dr. Hans van Willigen and Dr. Alejandro Bussandri at the
University of Massachusetts at Boston. If the transient absorption originates from a
ligand-based 3n,n* state, an EPR signal should be observed. On the other hand, no signal
is expected if the transient is a metal-based MLCT state because of the short spin-lattice
relaxation time associated with such a state. TREPR spectra following laser excitation
were recorded on a biphenyl analogue of 5-L-l and 5-ReAN-2 at 130 K and are shown in
Figure 3-19.
The biphenyl version of 5-L-l was used to model the expected 37i,7r* excited state
response. A broad resonance peak (~2000 gauss centered at g = 2) was observed. The
low-field half of this spectrum is an emission, and the high-field half is an absorption.
The resonance peak is assigned to the photoexcited 3n,n* state. This assignment is based
on the broad nature of the band, which occurs due to the dipole - dipole interaction
between the unpaired electrons of the triplet state.143 The E/A polarization pattern arises
from the singlet-triplet intersystem crossing process spin selectivity that populates the
three levels in the triplet manifold.

119
l 1 1 . 1 1 1 < 1 1 1 1 1 1 1 1 1 »—
1000 1500 2000 2500 3000 3500 4000 4500 5000
Bo [gauss]
Figure 3-19: Transient EPR spectra of 5-L-l (biphenyl analogue, dotted line) and
5-ReAN-2 (solid line) at 130 K in 1:1 toluene:chloroform solution.
A spectrum of 5-ReAN-2 at 130 K gives a similar but narrower resonance peak
(700 gauss at g = 2) with reverse polarization characteristics with respect to the biphenyl
5-L-l TREPR spectrum. The polarization difference suggests that even though the
resonance still originates from the 37t,7t* excited state, this state is reached via a different
pathway (i.e., through the metal MLCT state). If the excited state is mainly MLCT in
character, one would not expect to detect a signal due to very rapid spin-lattice relaxation
associated with the metal center. However, the observed signal-to-noise decrease and
reduction in spectral width could suggest that the 37t,7t* excited state may contain a small
amount of MLCT character. Nevertheless, the data support the conclusion that the
observed transient absorption does have significant 3n,n* character.

120
The slow-component amplitude decrease as temperature decreases in the 5-Re
complexes (Table 3-4) is an example of “delayed fluorescence,” which has been observed
in fullerenes144 and other ^-conjugated systems.115,145 Note that in the excited-state
equilibrium (Figure 3-18) the MLCT energy is slightly higher than the n,n* energy, as
seen in the low-temperature 5-Re emission spectra (Figure 3-6). Therefore, thermal
energy is needed in order to maintain equilibrium and produce the observed 3MLCT
luminescence. As temperature decreases, the available thermal energy decreases, driving
the equilibrium more to the n,n* state and decreasing the observed MLCT emission
component amplitude. Eventually, hardly any population remains in the 3MLCT state
after equilibration, resulting in a slow decay component which is barely detectable above
the instrument baseline.108,146 The 5-ReAN complexes cannot exhibit this same “delayed
fluorescence” behavior due to the larger energy difference between the two excited states.
Similar biexponential emission decays were readily observed in spectra of a
ruthenium-pyrene donor-acceptor complex.147,148 A series of emission decays at different
temperatures for this complex are shown in Figure 3-20. The ligand-based excited state
in this case is not emissive and is isoenergetic with the metal-based 3MLCT state. The
observed biexponential decays are due to an excited state equilibration, and the
temperature dependence (i.e., the long-lived component amplitude increases with
increasing temperature) illustrates 3MLCT “delayed fluorescence” via thermal back-
population. This data is very similar to the decays observed for the 5-Re complexes
(Figure 3-8).

121
Figure 3-20: Luminescence decays of [(bpy)2Ru(bpy_pyr)]2+ in 4:1 EtOH:MeOH at
various temperatures (Ref. 147). (a) 150 K; (b) 200 K; (c) 250 K.
In order to better understand the excited-state behavior of these complexes,
simulations were performed using a Runge-Kutta integrator.149 Decays of two excited
states in equilibrium were modeled with independent decay lifetimes of 150 ns (MLCT)
â– > T
and 9 ps ( n,n*). It was assumed that the MLCT state is the initially populated state.
When K<;q, the constant for equilibrium between the two excited states defined as
^ ti.ji*-» MLCT
, was 1-10, results exhibit the same 3MLCT emission biexponential decay
observed in the experimental results. Lifetimes of the two excited-state decays are also
equivalent, ranging from 100 to 300 ns. However, as Keq increased beyond 10, the
3MLCT emission decay rapidly goes to zero with very short lifetimes (< 5 ns), while the
3ti,7i* decay remains largely unchanged in intensity but considerably longer (5-6 ps).
These results mirror the 5-ReAN experimental data. Further quantitative fitting of our
data was not possible due to our limited time resolution in the emission lifetime and

122
transient absorption experiments. Typically, the fast lifetime decay was complete within
the span of just a few data points on our fastest time response settings.
Experimental
Oligomer and Complex Synthesis
The molecules and complexes in the 5-L oligomers and 5-Re complexes were
previously synthesized, and their synthesis is described in detail elsewhere.99’100
5-ReAN-2. 5-Re-2 (12 mg, 6.1 pmol) was dissolved in 20 mL methylene
chloride, whereupon 5 mL of CH3CN and AgOTf (12 mg, excess) was added. The
solution was stirred at room temperature overnight. A TLC (1:1 hexanes:CH2Cl2) on
silica showed two spots, Rf = 1 (5-ReAN-2) and Rf = 0.6 (5-Re-2). Additional stirring
and addition of acetonitrile produced the final product. AgCl was removed from the
sample solution by filtration through celite on a medium-porosity glass frit, and the
filtrate was reduced by rotary evaporation to produce the final product as a triflate salt.
Due to the small amount of material available, further purification was impractical. IR
(THF soln, cm'1), 1966, 2101, 2135 (u<>o), 2278 (uCsn).Í ESI-MS caled for
Ci3iHig2N307Re: 2096; found: 2053 (parent - CH3CN).
5-ReAN-3. This synthesis progressed in an analogous manner to the 5-ReAN-2
synthesis except that 5-Re-3 was used as the starting material. IR (THF soln, cm'1) 1967,
2097, 2133 (uc=o), 2280 (uc=n)- ESI-MS caled for Ci49Hi95N20nRe: 2416; found: 2414
(parent), 2372 (parent - CH3CN).
Í For comparison purposes, 5-Re-2 and 5-Re-3 in a KC1 pellet exhibit uc-o stretches at
1902, 1927, and 2025 cm'146

123
Photophysical Measurements •
All sample solutions studied are in either THF, 2-methyltetrahydrofuran (2-
MTHF), or CH2CI2. All solvents were distilled according to typical laboratory practices.
All photophysical studies were conducted in 1 cm square quartz cuvettes unless otherwise
noted. All room temperature studies were conducted on argon bubble-degassed solutions,
and all low temperature studies were conducted on solvent glasses degassed by four
freeze-pump-thaw cycles (ca. 10'4 Torr) unless otherwise noted. For the emission and
photothermal measurements, sample concentrations were adjusted to produce “optically
dilute” solutions (i.e., A < 0.20 at all wavelengths; typical final concentration is ca. 1.5 x
10'6 M). Transient absorption measurements were routinely performed on solutions with
higher concentrations (i.e., A « 0.8 - 1.0, ca. 7.5 x 10-6 M).
Steady state absorption spectra were recorded on either an HP 8452A diode-array
or Varian Cary 100 dual-beam spectrophotometer. Corrected steady state emission
measurements were conducted on a SPEX F-l 12 fluorimeter. Emission quantum yields
were measured by relative actinometry (chapter 2), with 9,10-dicyanoanthracene (Oem =
0.89) and perylene (Oem = 0.89) in ethanol as actinometers.97 Time-resolved emission
decays were observed with time-correlated single photon counting (FLT, Photochemical
Research Associates; Excitation filter/source: Schott UG-11/H2 spark (350 nm
maximum) or 405 nm IBH NanoLED-07 laser diode; Emission filter: 450 and 550 nm
(5-L oligomers) or 600 nm (5-Re complexes) interference filters). Lifetimes were
determined from the observed decays with DECAN fluorescence lifetime deconvolution
software.98 Low temperature emission measurements were conducted in 1 cm diameter
glass tubes contained in an Oxford Instruments cryostat connected to an Omega

124
CYC3200 automatic temperature controller. Transient absorption spectra were obtained
on previously described instrumentation,150 with the third harmonic of a Nd:YAG laser
(Spectra Physics GCR-14, 355 nm, 10 ns fwhm, 5 mJ pulse'1) as the excitation source.
Spectra for the 5-L oligomers were recorded on freeze-pump-thaw degassed solutions due
to their long lifetimes and the high propensity for oxygen to quench organic triplet excited
states. Primary factor analysis followed by first order (A -> B) least square fits of the
transient absorption data was accomplished with SPECFIT global analysis software.114
LIO AS and TRTL measurements were obtained with the setups described in chapter 2.
LIOAS data (average of four data acquisitions on fresh sample and reference solutions)
were obtained with both 1 and 5 MHz transducers, and LIOAS data deconvolution
analysis was performed with Sound Analysis software. ’
Time-resolved EPR measurements were conducted on a Varían E-9 X-band
spectrometer with a variable temperature attachment to allow data collection at 130 K.
The signal from the microwave bridge was fed into a PAR 162 dual channel boxcar
integrator via an HP461A high-frequency amplifier. The integrator signal was then fed
into a PC via a data acquisition board for signal processing and analysis.151 Samples were
excited at 355 nm with a Nd:YAG laser. Sample solutions were prepared in 1:1
toluenexhloroform and freeze-pump-thaw degassed.
Electrochemical Measurements
All electrochemical measurements were conducted on THF solutions with 0.1 M
tetrabutylammonium hexafluorophosphate (TBAH, Aldrich) as the supporting electrolyte.
Cyclic voltammetry measurements were performed on nitrogen bubble-degassed
solutions with a BAS CV-27 Voltammograph and MacLab Echem software or a BAS

125
CV-50W Voltammetric Analyzer and accompanying software. Platinum disk and glassy
carbon working electrodes, platinum wire auxiliary electrode, and silver wire quasi¬
reference electrode were used, and potentials were corrected to values versus SCE via an
internal ferrocene standard. A scan rate of 100 mV sec'1 was employed in all
measurements.
Langmuir-Blodgett Film Preparation
A KSV 2000 system (Stratford, CT) was used in combination with a homemade,
double barrier Teflon trough for the LB film preparation. The surface area of the trough
is 343 cm2 (36.5 cm x 9.4 cm). A platinum Wilhelmy plate, suspended from a KSV
microbalance, measured the surface pressure. Subphases were pure water with a
resistivity of 17-18 MQ cm'1 produced from a Bamstead NANOpure (Boston, MA)
purification system. LB films were prepared from premixed chloroform solutions of
5-Ru-2 and 5-L-3 (typical concentrations were 2 x 10'4 M). Spreading volumes of 100 to
150 pL were used, and the films were compressed to and maintained at a pressure of 20
mN m'1 for film transfer. Glass substrates were drawn through the monolayer at a rate of
8 mm min'1 during the film transfer.

5-5' MONOPHENYL OLIGOMER PHOTOPHYSICS
Introduction
The photophysical work on the 5-L oligomers and 5-Re complexes led to insight
concerning the nature of the interactions between rc-conjugated systems and MLCT
chromophores, prompting additional oligomer synthesis and subsequent photophysical
study. A series of oligomers (5-LP oligomers) were synthesized containing monophenyl
subunits in the conjugated backbone in contrast to the biphenyl units used in the 5-L
oligomers. These oligomers contain a “core” consisting of a 5,5’-(2,2 ’ -bipyridyl) unit and
primary repeat units on either side containing 1,4-diethynylbenzene and dialkoxybenzenes
and were synthesized with similar synthetic methodologies used for the 5-L
oligomers.64,99 Complexes (5-ReP complexes) were synthesized ligating these oligomers
to the -Re'(CO)3Cl chromophore.99,100 The structures of the 5-LP oligomers and 5-ReP
complexes are shown in Figure 4-1. Extensive photophysical and photo thermal studies
were conducted on these molecules, and the results are presented in this chapter.
Results
Several photophysical parameters from various measurements are presented for
the 5-LP oligomers and 5-ReP rhenium complexes in Tables 4-1 and 4-2, respectively.
The individual measurements are discussed below.
126

127
OR OR
5-LP-2: M = -
5-ReP-2: M = Re'(CO)3CI
OMe OR OR OMe
Figure 4-1: 5-LP oligomer and 5-ReP rhenium complex structures.
Table 4-1: 5-LP oligomer photophysics.
5-LP-2
5-LP-3
5-LP-4
Absorption
^max / nm
334 (5.45)
338 (7.93)
334(12.7)
(6max / 104 M'1 cm'1)
396 (9.13)
406(14.6)
414(25.6)
Emission
^max, 298 K / nm
460
449
452
^max, 80 K / nm
471
473
471
em
0.72
0.77
0.87
kr/ 108 s'1
6.55
8.42
13.9
knr + kjsc / 108 S''
2.55
2.52
2.08
TA
1298 K / PS
375
410
277
Note: Measurements were conducted on freeze-pump-thaw degassed THF solutions. Additional
experimental conditions are discussed in the text.

128
Table 4-2: 5-ReP rhenium complex photophysics.
5-ReP-2
5-ReP-3
5-ReP-4
Absorption
^max/nm
331 (6.51)
348(10.8)
338(14.7)
(emax / 104 M"' cm"1)
438 (6.78)
442(10.2)
393 (18.7)
Emission
^•max, 298 K / nm
659
650
646
Amax, 80 K / nm
659
652
579,666
TA
*298 K / OS
123
181
164
Electrochem
EÍ/2 / V vs. SCE
-0.79a
-0.82b
C
-0.79b
Note: Measurements were conducted on argon bubble-degassed THF solutions. Additional experimental
conditions are discussed in the text. aPt disc working electrode. bGCE disc working electrode. cNo
resolvable wave was obtained for 5-ReP-4.
Absorption Spectra
Absorption spectra were recorded on dilute THF solutions of the various
oligomers and rhenium complexes, and molar absorptivity values (s, M'1 cm"1) were
calculated based on (3-1). Absorption spectra for the 5-LP oligomers and 5-ReP
complexes are shown in Figure 4-2, and absorption maxima for all oligomers and
complexes are listed in Tables 4-1 and 4-2, respectively.
The oligomer spectra exhibited the same two n,n* transitions observed in the 5-L
oligomers (Figure 3-2), and the 5-LP absorption maxima are relatively equivalent with
analogous 5-L oligomers. Note that the band energies red-shift with increasing
conjugation length, which is counter to the consistent maximum observed in the 5-L
oligomers and suggests less-efficient ^-conjugation disruption with the monophenyl
subunits compared to the twisted biphenyl subunits. The rhenium complex spectra
exhibited the same two n,n* transitions red-shifted from uncomplexed oligomer values,

129
and 5-Re and 5-ReP absorption maxima are equivalent. This shift reflects increased
conjugation due to forced bipyridine planarity via complexation as discussed in chapter 3.
The low-energy band remains constant in the complex spectra, while the high-energy
band red-shifts with increasing oligomer length. As explained previously, this
observation suggests the existence of isolated “central” and “peripheral” chromophores
within the same molecule as a result of oligomer backbone conjugation breaks.
Furthermore, 5-ReP-4 (like 5-Re-4) exhibits absorptions seen both in the 5-LP oligomers
(338 and 393 nm) and 5-ReP complexes (« 450 nm shoulder), further confirming the
isolation of multiple chromophores in a single complex. Like the 5-Re spectra, any
MLCT-based absorptions are obscured by the more intense oligomer 7t,7t* transitions.
Emission Spectra
The 5-LP oligomer emission spectra in optically dilute 2-MTHF solutions at
temperatures ranging from room temperature to 80 K are shown in Figure 4-3. Emission
maxima at room temperature and 80 K are listed in Table 4-1. The oligomer room
temperature fluorescence spectra exhibited the same strong band assigned to the long-axis
polarized '71,71* state in the 5-L spectra (Figure 3-3). The fluorescence maximum remains
constant throughout the oligomer series and is slightly blue-shifted relative to the 5-L
oligomer maxima. The (0,1) shoulder band intensity clearly decreases relative to the (0,0)
band as the oligomer size increases, reflecting an electron-vibration coupling decrease
with increasing oligomer length due to increased '71,71* state delocalization.29 This
coupling decrease is smaller than that observed for the 5-L-2, since 5-LP-2 does not
exhibit the (0,1) shoulder. The difference is likely due to the smaller size of the 5-LP-2
oligomer, although the size difference is not very large. No phosphorescence was

130
detected at low temperatures for any of the 5-LP oligomers. Emission quantum yields
were measured for the oligomers using (2-17), and calculated values are listed in Table
4-1. Note that the quantum yields increase as the oligomer size increases. While
quantum yields agree well for 5-L-2 and 5-LP-2, the 5-L-3 and 5-L-4 quantum yields are
smaller than their monophenyl counterparts.
300 350 400 450 500 550
Wavelength / nm
Figure 4-2: Absorbance spectra in THF. (a) 5-LP oligomers; (b) 5-ReP complexes.

131
400 450 500 550 600 650
Wavelength / nm
Figure 4-3: Emission spectra of the 5-LP oligomers in 2-MTHF (360 nm excitation) at
various temperatures ranging from 298 to 80 K. Emission intensity decreases with
decreasing temperature except as noted, and spectra are in 30 K increments, (a) 5-LP-2;
(b) 5-LP-3; (c) 5-LP-4 (note unique low temperature trends).
All oligomer fluorescence red-shifts with decreasing temperature, exhibiting the
same behavior displayed by the 5-L oligomers. This observation supports the aggregation
conclusions discussed in chapter 3. One of the goals of studying the 5-LP oligomers was
to see if the monophenyl subunit might lessen the initial intramolecular aggregation effect
by removing the biphenyl subunit that is restricted by sterics. However, the

132
photophysical data clearly indicates that similar aggregational effects are observed for
both the biphenyl and monophenyl oligomers. Therefore, it is believed that the long alkyl
side chains rather than the oligomer backbone structure provides the major impetus for
the initial “intramolecular excimer” formation process (Figure 3-17), although the
monophenyl-based backbone exhibits some of the same rotational flexibility observed in
the biphenyl-based oligomers. One interesting difference in the 5-LP oligomers,
however, was observed in the 5-LP-4 temperature-dependent behavior. After the 2-
MTHF sample solution freezes (ca. 170 K), the excimer-based emission increases in
intensity and remains at a constant energy. This observation is duplicated to a much
lesser extent in the other 5-LP oligomers and is similar to the temperature dependence
typically observed in oligomer chromophores.108
The 5-ReP complex emission spectra in optically dilute 2-MTHF solutions at
temperatures ranging from 298 to 80 K are shown in Figure 4-4. Emission maxima at
298 and 80 K are listed in Table 4-2. As observed for the 5-Re complexes, a weak
emission corresponding to free oligomer n,n* fluorescence was observed in the complex
samples and is considered a trace free oligomer impurity. The rhenium complexes
exhibited a weak, low-energy emission that increased in intensity with decreasing
temperature similar to the 5-Re complexes (Figure 3-5). The emission band structure at
80 K again appears to consist of an overlapping structureless 575 - 600 nm band that
blue-shifts with decreasing temperature and structured 650 nm band that remains constant
with decreasing temperature. The structureless band increases in intensity with increasing
oligomer size, leading to a clear resolution of the two emission components in the

133
5-ReP-4 spectrum. Attempts were made to measure the emission quantum yield of the
5-ReP complexes, but they were too weak to be effectively measured (< 1 O'4).
The superimposed emission spectra at low temperatures warranted excitation
polarization studies to see if behavior similar to 5-Re-3 was observed (Figure 3-6).
Spectra were collected on an 80 K 2-MTHF 5-ReP-3 solution at various emission
wavelengths. Excitation spectra and r(A.) values are shown in Figure 4-5 along with the
80 K emission spectrum that indicates the examined wavelengths. The high-energy
structureless shoulder exhibits a high anisotropy value (0.3 maximum) that decreases with
decreasing excitation wavelength, exhibiting a typical anisotropy behavior for similar
absorbing and emitting excited states.109 Anisotropies recorded at the structured emission
maximum exhibit a lower value (0.07) that does not vary across the excitation spectrum,
indicating nearly unpolarized emission light and a large triplet phosphorescence
component in the emission at that wavelength. This polarization data exhibits trends
identical to those observed for 5-Re-3, so the conclusions stated earlier for the low
temperature emission apply. Again, the structured emission is oligomer-based 37i,7i*
phosphorescence and the overlapping structureless emission is metal-based MLCT
luminescence. It is clear that changing from biphenyl to monophenyl subunits does not
alter the temperature-dependent emission behavior of the complex other than increasing
the intensity of the MLCT luminescence. This increase may be due to the increased
rigidity or planarity of the monophenyl-based oligomer backbone, which might lessen the
likelihood of nonradiative decay via molecular rotation and account for the linear
relationship between MLCT intensity and oligomer length.

134
Figure 4-4: Emission spectra of the 5-ReP complexes in 2-MTHF (450 nm excitation) at
various temperatures ranging from 298 to 80 K. Emission intensity increases with
decreasing temperature, and spectra are in 30 K increments, (a) 5-ReP-2; (b) 5-ReP-3;
(c) 5-ReP-4.

135
0.4
0.3
0.2
0.1
0.0
0.4
0.3
0.2
0.1
0.0
300 350 400 450 500 550
Wavelength / nm
Figure 4-5: Excitation (dashed line) and excitation polarization (solid line) r(X) spectra at
80 K of 2-MTHF 5-ReP-3 solution at various emission wavelengths.
Emission Lifetimes
Emission decay lifetimes were recorded for the 5-LP oligomers in 2-MTHF at
various temperatures and emission wavelengths. Both monoexponential and
biexponential decays were observed, and lifetime results are listed in Table 4-3.

136
Table 4-3: Variable temperature emission decay times of the 5-LP oligomers.
Oligomer11
T/K
«i
450 nm Emission
Tj / ps a2
x2/ps
a,
550 nm Emission
ti / ps a2
T2/pS
5-LP-2
298
1
1099.0
-
-
1
1138.0
-
-
80
1
967.0
-
-
0.997
352.0
0.003
7707.0
5-LP-3
298
1
914.7
-
-
-
-
-
-
180
1
785.5
-
-
0.974
1326.4
0.026
6701.7
80
-
-
-
-
0.981
1332.4
0.019
7863.4
5-LP-4
298
1
627.4
-
-
1
627.2
-
-
80
0.950
614.8
0.050
4529.3
0.970
881.8
0.030
4346.2
a2-MTHF solutions; 405 nm excitation. Biexponential decays were calculated based on (3-3). Errors for
the fit parameters are ± 5%.
On the blue side of the fluorescence (450 nm), decay kinetics are single
exponential, decrease in lifetime with decreasing temperature and are roughly equivalent
to the 5-L oligomer emission lifetimes (Table 3-3). On the red side of the fluorescence
band (550 nm), decays are monoexponential at room temperature (except 5-ReP-4) and
biexponential with a long-lived component (4-7 ns) at reduced temperatures. These
observations duplicate the 5-L oligomer data and are reminiscent of excimer species
formation in solution at reduced temperatures via extended aggregation, resulting in the
longer-lived emission. Values for kr and knr + kisc at 298 K were also calculated based on
(4-1) and are listed in Table 4-1.
kr =
*l*em
(4-la)
1, _ kr0 em)
Knr ^ Kisc - ,
t em
(4-lb)

137
The kr values clearly increase while knr + k¡sc decreases as oligomer size increases,
due to the increase in electron delocalization afforded by the size increase. These values
and trends are very similar to those determined for the 5-L oligomers (Table 3-10),
suggesting similar excited-state manifolds for the two oligomer series.
Emission decay lifetimes were recorded for the 5-ReP complexes in 2-MTHF at
various temperatures, and lifetime results are listed in Table 4-4.
Table 4-4: Variable temperature emission decay times of the 5-ReP complexes.
Complex3
T/K
OCi
550 nm Emission
Xj / ns a2
x2 / ns
a,
650 nm Emission
Xi / ns a2
x2 / ns
5-ReP-2
298
0.999
0.476
0.001
375.4
0.996
0.476
0.004
255.0
171
0.999
0.202
0.001
56.4
0.996
4.961
0.004
2644
80
0.999
0.202
0.001
91.5
0.995
4.961
0.005
2801
5-ReP-3
298
0.999
0.200
0.001
86.78
0.995
1.85
0.005
754.7
172
0.999
0.200
0.001
48.89
0.995
10.0
0.005
3657
80
0.997
0.200
0.003
7.363
0.997
10.0
0.003
5097
5-ReP-4
298
-
-
-
-
0.996
0.736
0.004
176.9
80
1
1.103
-
-
> 0.999
1.107
<0.001
b
“2-MTHF solutions; 405 nm excitation. Biexponential decays were calculated based on (3-3). Errors for
the fit parameters are ± 5%. bDecay component was too weak to accurately measure the lifetime.
Emission decays of the structured 7t,7t* phosphorescence (650 nm) are
biexponential at all temperatures and characterized by a large amplitude, short-lived
component (x » 1 - 4 ns at room temperature, a > 0.95) and a low amplitude longer-lived
component (x = 250 - 750 ns at room temperature, a » 0.005). Only the long-lived
component shows significant temperature dependence, increasing to a lifetime of several
microseconds at 80 K. As the oligomer size increases, the amplitude of the longer-lived

138
component decreases to the point that it is too weak to accurately measure in 5-ReP-4 at
80 K. These lifetimes (even at room temperature) are longer than the analogous 5-Re
complex emission lifetimes, suggesting a lower n,n* energy in the monophenyl-based
oligomer complexes that would draw more electronic population from the 3MLCT state
and upset the excited-state equilibrium.
Furthermore, 3MLCT luminescence emission decays (550 nm) also exhibit
biexponential decays, but the majority of the decay (99.9% of the total amplitude) is
represented by a rapid decay component. The long-lived component is much shorter (t <
100 ns at room temperature) and is so small in amplitude that its lifetime is difficult to
accurately determine. This behavior is similar to the lifetime data of the 5-ReAN
complexes in chapter 3, where the shorter lifetime stemmed from the “pure” 3MLCT
excited state after equilibrium disruption. Clearly, the monophenyl-based complexes
exhibit better separation of the two excited-state emissions than the biphenyl-based
complexes. Alternatively, 5-LP impurities in the 5-ReP samples could lead to the short
550 nm lifetimes originating from free ligand fluorescence.
Transient Absorption Spectra
Transient absorption spectra were recorded for all the oligomers and complexes in
THF solutions. Transient absorption spectra for the 5-LP oligomers are shown in Figure
4-6. Excited state lifetimes obtained from factor analysis and global decay fitting114 are
listed in Table 4-1. Equivalent first order decays were observed for all features of the
various transient absorption spectra. These spectra are very similar to their 5-L analogues
j|4 t t ^
Emission lifetimes for the 5-Re complexes were independent of the probed wavelength.

139
(Figure 3-8), with all oligomers exhibiting long-axis n,n* ground state absorption
bleaching and a broad, long-lived excited-state absorption extending into the near-IR.
Excited state lifetimes are very long (300 - 400 ps), which is typical for organic
triplets. These transients, like the corresponding 5-L spectral features, are assigned to
oligomer n,n* excited states.
Transient absorption spectra for the 5-ReP complexes in THF solutions are shown
in Figure 4-7. Excited state lifetimes obtained from factor analysis and global decay
fitting114 are listed in Table 4-2. Generally, equivalent first order decays were observed
for all spectral features. However, the 450 nm bleach exhibited biexponential decay in
certain samples with a rapid decay component (x < 1 ns) and longer-lived decay
component with lifetimes that corresponded to the other transients in the spectrum. This
behavior is due to trace 5-LP free oligomer impurities as described in the previous
chapter. Obtained spectra are very similar to the 5-Re complexes (Figure 3-9), with a 450
nm ground state bleach and transient absorptions at 500 and 700 nm stretching into
the near-IR. The transient decay lifetimes for 5-ReP-2 and 5-ReP-3 are shorter than the
room temperature 650 nm emission decay lifetime shown in Table 4-4. This observation
further suggests that the 650 nm emission is mainly 37x,tc* phosphorescence in nature due
to its longer lifetime. While the transient absorption spectra stem from this same excited
state, their lifetimes may be shorter due to the influence of the excited-state equilibrium
on the lifetime. Furthermore, the transient absorption may have an MLCT contribution,
which would shorten the lifetime. This explanation is definitely possible for 5-ReP-4,
which has equivalent TA and emission lifetimes and a different, flatter TA excited-state
absorption, which may be indicative of an 3MLCT state. Based on these results and the

140
5-Re spectra, the transients are assigned to oligomer-based 3n,n* transitions (except for
5-ReP-4) with the assumption that an excited-state equilibrium exists between the 3n,n*
and 3MLCT states as seen in the 5-Re complexes.
Electrochemistry
Cyclic voltammetry was performed on the 5-ReP complexes in THF with 0.1 M
TBAH as the supporting electrolyte. Quasi-reversible reduction waves were observed in
all cases (except 5-ReP-4), and reduction half-wave potentials are listed in Table 4-2.
Note that the reduction potential is similar for the two complexes but about 0.1 V less
negative (i.e., easier to reduce) than the analogous 5-Re complexes, which implies that
the oligomer conjugation extends to a greater degree in the monophenyl-based oligomer
complexes to facilitate easier electron addition to the complexed oligomer.
Discussion
For the majority of the presented photophysical measurements, the monophenyl
and biphenyl subunit-based oligomers and rhenium complexes have very similar
properties. However, some subtle differences warrant further consideration. Since the
oligomers differ only by the presence of monophenyl instead of biphenyl subunits, the
photophysical differences must stem from this change. The biphenyl subunit is more
likely to be twisted due to steric interactions of the a-hydrogens on adjacent phenyl rings,
producing conjugation breaks as described in chapter 1 and involved in much of the
photophysics presented in chapter 3. While the monophenyl-based oligomers would not
have this same steric hinderance, some flexibility and rotational ability remains in the
monophenyl-based backbone to produce some of the results described in this chapter.

141
0)
o
c
ra
.Q
L_
O
w
n
<
<
0.02
0.01
0.00
-0.01
-0.02
-0.03
0.02
0.01
0.00
-0.01
-0.02
-0.03
0.02
0.01
0.00
-0.01
-0.02
-0.03
400 500 600 700 800
Wavelength / nm
Figure 4-6: Transient absorption spectra of the 5-LP oligomers in ffeeze-pump-thaw
degassed THF solutions. Arrows show the spectral trend with increasing time after laser
excitation, (a) 5-LP-2 (Transients are 80 ps increments after laser excitation; (b) 5-LP-3
(Transients are 40 ps increments after laser excitation); (c) 5-LP-4 (Transients are 40 ps
increments after laser excitation).

142
Figure 4-7: Transient absorption spectra of the 5-ReP complexes in argon
bubble-degassed THF solutions. Arrows show the spectral trend with increasing time
after laser excitation, (a) 5-ReP-2 (Transients are 160 ns increments after laser
excitation; (b) 5-ReP-3 (Transients are 80 ns increments after laser excitation);
(c) 5-ReP-4 (Transients are 80 ns increments after laser excitation).

143
The 5-LP oligomer absorption spectra (Figure 4-2) exhibit red-shifting with
increasing oligomer length, indicating that the monophenyl subunit is less effective in
restricting backbone delocalization. The twisted biphenyl subunits in the 5-L oligomers
prevent this extended delocalization and lead to the constant absorption maxima across
the oligomer series (Figure 3-2). However, the 5-Re and 5-ReP complexes share similar
absorption spectral trends, suggesting the isolation of organic and metal-based
chromophores in the same oligomer. It is possible that the forced planarity of the central
bipyridine upon complexation may induce oligomer twisting in the 5-LP oligomers that
does not exist in the unligated oligomer.
In order to better understand the differences between the two oligomer series,
literature precedents are investigated with an interesting result. The absorption spectrum
of didodecoxy-substituted poly(phenyleneethynylene) in THF solution (Figure 1-3)
exhibited a 425 nm maximum.? Furthermore, model trimer and pentamer oligomers with
the same repeat structure feature absorption maxima at 376 and 418 nm, respectively.25
Clearly, a red-shift is observed with increasing oligomer size, which is replicated in our
oligomers to a lesser degree. The smaller red-shift in the 5-LP oligomers compared to
the PPE work may be due to the alkyl side-chain size increase to an eighteen-carbon
chain. This increase, coupled with the presence of alkyl chains on only half the phenyl
rings in the 5-LP oligomer backbone, may provide a thermodynamic impetus for
backbone twisting. The alkyl-substituted phenyl rings may twist in unison, while the
non-substituted rings may resist this movement and twist independently (or vice versa).
Unfortunately, very little precedent is found that addresses this PPE backbone twisting
issue.

144
Note that the 5-LP fluorescence maximum is blue-shifted 5 nm from analogous
5-L values and remains fairly constant across the oligomer series, suggesting that the
'71,71* excited state is higher in energy for the 5-LP oligomers. The different conclusions
presented by the absorption (more delocalized excited state) and emission (higher excited
state energy) spectra suggest that the initial photoexcited state probed by the absorption
spectra and the lower-energy emitting state are structurally different, perhaps due to a
change in oligomer conformation (i.e., twisting or canting of the various phenyl rings).
The higher 5-LP oligomer '71,71* energy should result in a higher emission
quantum yield based on the energy gap law. The quantum yields for 5-L-2 and 5-LP-2
are identical, which is not surprising since these two oligomers have identical
chromophores if the 5-L-2 biphenyl subunits are twisted. For 5-LP-3 and 5-LP-4, higher
quantum yields are observed than their biphenyl analogues, confirming this conclusion.
Recall also that the emission quantum yield increases with increasing oligomer size in the
5-LP oligomers, which is opposite of the trend observed in the 5-L oligomers. The
reversed trend is surprising, since the greater delocalization in the 5-LP oligomers should
increase ¡sc and decrease (|)em. The propensity of these oligomers to aggregate in solution
might lead to the increased quantum yields, since aggregates would erroneously increase
the measured value.
The unique temperature-dependent emission of 5-LP-4 (Figure 4-3) is interesting,
as the excimer exhibited spectral trends (intensity increase with decreasing temperature)
typically observed for organic molecules in the 2-MTHF glass. This same trend is
observed for the other 5-LP oligomers, but the intensity increase is very small compared
to 5-LP-4. The greater response observed for this oligomer could also be due to the

145
increased ridigity of the oligomer backbone due to the monophenyl subunits, which might
inhibit efficient aggregate formation and impair the non-radiative energy transfer decay
pathway. The mixed alkyl chain lengths of 5-LP-4 might further contribute to this effect,
as solvent pockets could be trapped within the aggregate and lessen its ability to quench
the monomer fluorescence.
The 5-ReP-4 complex is unique in the sense that it has a different transient
absorption spectrum (Figure 4-7). The “flatter” nature of the excited-state absorption is
less indicative of the 37r,7i* excited-state absorption observed for all the other biphenyl
and monophenyl-based free oligomers and rhenium complexes, which leads to the
conclusion that this transient may originate from the 3MLCT stated It is unclear why
5-ReP-4 would have this different excited-state behavior, as 5-Re-4 did not exhibit
results counter to the trends set forth by the rest of its complex series in chapter 3. The
differing sidechain structure of 5-ReP-4 is not likely to alter the metal-based excited state
energetics, but this is the only structural difference in this complex. Further studies,
including time-resolved infrared spectroscopy, will hopefully better elucidate this excited-
state behavior.
Experimental
Oligomer and Complex Synthesis
The 5-LP oligomers and 5-ReP complexes were previously synthesized, and their
synthesis is described in detail elsewhere.99,100
^ A similar TA spectrum is seen for P4-Os in chapter 6 (Figure 6-12), which assists in the
5-ReP-4 assignment.

146
Photophysical Measurements
All sample solutions studied were in either THF or 2-MTHF. All solvents were
distilled according to typical laboratory practices. All photophysical studies were
conducted with the same instrumentation and techniques described in chapter 3.
Electrochemical Measurements
All electrochemical measurements were conducted on THF solutions with TBAH
as the supporting electrolyte. Cyclic voltammetry measurements were performed with the
same procedures on the same instrumentation described in chapter 3.

4,4' OLIGOMER PHOTOPHYSICS
Introduction
After extensive photophysical work with the linear 5,5’-substituted oligomers, a
different oligomer geometry which could significantly affect its photophysics was
considered. A “bent” oligomer series, where the ethynylene substitutions on the central
2,2’-bipyridine occur at the 4,4’ positions was chosen for experimentation. This position
change is significant in the sense that the conjugated oligomer periphery is now in line
with the rhenium bipyridine MLCT dipole. Also, the overall dipole moment and
wavefunction of the oligomer itself will change by this structural shift, which might allow
better ligand and metal based excited state resolution than the 5,5’ oligomer rhenium
complexes presented in chapters 3 and 4. Previous studies16152 on n-conjugated polymers
showed that backbone structure can have a large effect on the excited state energy
manifold. Therefore, three “bent” PPE-type oligomers (4-L-l, 4-L-2, and 4-L-3) were
synthesized," along with complexes made with the Re^CO^Cl (4-Re-l, 4-Re-2, 4-Re-3)
and ReI(CO)3(NCCH3)+ (4-ReAN-3) chromophores. All the structures discussed in this
chapter are illustrated in Figure 5-1.
Results
Various photophysical parameters from many different measurements for the 4-L
oligomers and 4-Re rhenium complexes are listed in Tables 5-1 and 5-2, respectively.
147

148
All the oligomers and rhenium complexes were soluble in THF, 2-MTHF, and CH2C12 to
similar degrees as the 5,5’-substituted oligomers and complexes. No solubility
improvement was observed in more polar solvents.
4-Re-1: M = Re'(CO)3CI
4-Re-2: M = Re'(CO)3CI
4-Re-3: M = Re'(CO)3CI
4-ReAN-3: M = Re'(CO)3(NCCH3)+OTr
Figure 5-1: 4-L oligomer and 4-Re complex structures.

149
Table 5-1: 4-L oligomer photophysics.
4-L-l
4-L-2
4-L-3
Absorption
A™«/nin
296 (4.56)
320 (9.84)
332 (9.51)
(emax / 104 M'1 cm*1)
346 (2.67)
384(10.4)
388 (12.9)
Emission
^max, 298 K^m
415
422
426
^max, 80 K / nm
430,614
427,614
433
^em
0.77
(0.9 l)a
(0.96)a
TA
"t298 K / M-S
166.4
231.3
348.1
Note: Measurements were conducted on freeze-pump-thaw degassed THF solutions. Additional
experimental conditions are discussed in the text. “Values are erroneously high, see text for details.
Table 5-2: 4-Re rhenium complex photophysics.
4-Re-l
4-Re-2
4-Re-3
4-ReAN-3
Absorption
A^nax ! nm
314(4.31)
324 (7.30)
340(11.1)
343 (7.70)
(smax/104 M'1 cm1)
378 (2.25)
408 (5.00)
408 (8.25)
425 (4.92)
Emission
^max, 298 K / nm
670
678
615
620
kmax,80K/nm
610
609
621
617
^em
0.0032
0.0044
0.0046
<0.001
TA
*298 K / OS
37
183.4
329.7
33800
Electrochem
Ef®2 / V vs. SCE
-0.94a
-0.91b
-0.89a
N/A
-0.94a
Note: Measurements were conducted on argon bubble-degassed THF solutions (except 4-ReAN-3 transient
absorption measurements, which were CH2C12 solutions). Additional experimental conditions are discussed
in the text. bGCE disc working electrode. cPt disc working electrode.
Absorption Spectra
Absorption spectra of the 4-L oligomers and 4-Re rhenium complexes in THF
solutions, with absoprtivity values calculated based on (3-1), are shown in Figure 5-2.
Absorption maxima are listed for the oligomers and complexes in Tables 5-1 and 5-2,
respectively.

150
Figure 5-2: Absorption spectra in THF. (a) 4-L oligomers; (b) 4-Re complexes.
The ligand absorption spectra exhibited two intense n,n* absorption bands that are
similar to those observed in the 5-L and 5-LP oligomers (Figures 3-2 and 4-2). However,
the 4-L oligomers are blue-shifted by 20 nm with respect to the “linear” oligomers. The
absorptivity values remain high, which is expected for conjugated organic systems. The
lowest energy band experiences a significant red-shift from 4-L-l to 4-L-2 but does not
exhibit further significant shifting in 4-L-3. This trend mirrors the 5-L spectral data, so it
can be concluded that conjugation breaks also occur in the 4-L oligomers. This

151
conclusion is not surprising since the structural repeat units do not change from the
“linear” species.
The rhenium complex absorption spectra exhibited two strong bands that red-shift
about 20 nm from the free ligand spectra. These bands are the 71,71* oligomer absorptions
observed in the 4-L spectra, and the red-shift is due to complexation of the rhenium
chromophore and the subsequent conjugation increase. This observation is similar to the
5-Re and 5-ReP spectra, but the shift is smaller for the 4-Re complexes. In the 4-Re-l
spectrum, a distinct shoulder is observed on the red side of the low-energy absorption
band. This shoulder is the singular evidence of an unobscured MLCT absorption seen for
the PPE-type oligomer complexes, as the 71,71* transitions in the remaining complexes are
too intense to permit its observation. Note that the 4-Re complex low-energy absorption
band continues to increase in intensity and red-shift with increasing oligomer size. The
5-Re complexes, however, exhibit constant low-energy absorptions, suggesting a
“constant” chromophore in the middle of the oligomer (Figure 3-2). Obviously, the 4-Re
central chromophore is not efficiently isolated from the “peripheral” chromophores at the
oligomer ends, which may influence the additional red-shift seen in the 4-L spectra.
Another possibility is that the 4-L oligomer is now in line with the MLCT transition
dipole, which may influence the transition energy.
Emission Spectra
The 4-L oligomer emission spectra in optically dilute 2-MTHF solutions at
temperatures ranging from room temperature to 80 K are shown in Figure 5-3, and the
emission maxima at room temperature and 80 K are listed in Table 5-1.

152
400 450 500 550 600 650
Wavelength / nm
Figure 5-3: Fluorescence spectra of the 4-L oligomers in 2-MTHF (350 nm excitation) at
temperatures varying from 298 to 80 K. The emission intensity trends as temperature
decreases are indicated by the arrows, and individual spectra are in 30 K increments.
Inset spectra show 80 K phosphorescence, (a) 4-L-l; (b) 4-L-2; (c) 4-L-3.
The spectra exhibit strong n,n* fluorescence that is analogous to the 5-L and 5-LP
spectra (Figures 3-3 and 4-3). The emission maxima do not vary across the oligomer
series, suggesting that the '71,71* energy remains constant with increasing oligomer size.
The (0,1) shoulder also decreases in intensity relative to the (0,0) band as oligomer size
increases, which duplicates the 5-L results and again suggests increased '71,71*

153
9Q
delocalization in the larger oligomers. However, unlike the 5-L and 5-LP oligomers
phosphorescence was observed at low temperatures for oligomers 4-L-l and 4-L-2 as a
structured emission with a 614 nm maximum. Note that the position of this emission is
very similar to that observed in the 5-Re and 5-ReP complexes, which was assigned to
the oligomer 37i,7i* state (Figures 3-5 and 4-4). The phosphorescence observed for 4-L-l
and 4-L-2 is clearly due to a different excited-state wavefunction and possible spin-orbit
coupling increase resulting from the “bent” geometry.
The oligomer fluorescence red-shifts with decreasing temperature and decreases
in intensity, resulting in a broad low temperature emission. Oligomer 4-L-l, however,
exhibits a unique intensity increase concurrent with the red-shift from 298 to 200 K
before a dramatic fluorescence quenching at 190 K coinciding with phosphorescence
initiation. This photophysical trend is identical to the observations for the 5-L and 5-LP
oligomers that was concluded to be a combination of intra- and inter-molecular energy
transfer through conformation changes and aggregation. This process, however, appears
to be superceded in 4-L-l and 4-L-2 by the phosphorescence emission decay, since the
fluorescence almost entirely disappears in 4-L-l and is greatly reduced in 4-L-2 at 80 K.
Furthermore, the initial appearance of phosphorescence occurs at a higher temperature in
4-L-l (190 K) than 4-L-2 (160 K). These observations suggest that the competition
between excited state decay through either phosphorescence or nonradiative energy
transfer is dependent upon the oligomer size. In 4-L-l, phosphorescence is the most
favorable decay pathway, leading to the pronounced emission at reasonably high
temperatures. The larger size and introduction of long alkyl side chains in 4-L-2
increases the favorability of energy transfer deactivation, leading to a weaker

154
phosphorescence that does not appear until lower temperatures. The oligomer size is
further increased in 4-L-3, where aggregation and conformation-induced energy transfer
is now the favored decay pathway and phosphorescence is no longer observed.
Emission quantum yields were measured for the oligomers, and calculated values
are listed in Table 5-1. The quantum yields are again very high, which is typical of rigid
organic chromophores. However, the high values were difficult to accurately measure,
and several attempts were made to achieve consistent results. This problem may result
from oligomer aggregation in solution. The reported values are averages of several data
sets, but it will be clear in calculations below that the 4-L-2 and 4-L-3 yields are
erroneously high.
The 4-Re complex emission spectra in optically dilute 2-MTHF solutions at
temperatures varying from 298 to 80 K are shown in Figure 5-4. The emission maxima at
room temperature and 80 K are listed in Table 5-2. Again, very weak emssion was
observed in all the rhenium complex samples that corresponded to the free oligomer
fluorescence. This emission was considered to be a trace impurity. The 4-Re complexes
exhibited a weak, broad emission that increases in intensity with decreasing temperature,
which repeats to the 5-Re and 5-ReP spectral trends. Emission intensities were high
enough to successfully measure their quantum yield, and calculated values are listed in
Table 5-2. The yields are rather low, but these are typical of (bipyridine)Re‘(CO)3Cl
complexes.41 The ability to measure the “bent” complex quantum yields may stem from
higher 4-L excited-state energy levels, which increases the MLCT energy gap.

155
(A
**
C
Z)
£
rs
k-
V
15
<
(A
C
0)
c
c
o
(A
(A
E
LU
500 550 600 650 700 750 800
Wavelength / nm
Figure 5-4: Emission spectra of the 4-Re rhenium complexes in 2-MTHF (400 nm
excitation) from 298 to 80 K. The emission intensity decreases as temperature increases,
and individual spectra are in 20 K increments for all complexes except 4-Re-3, which is
in 30 K increments, (a) 4-Re-l; (b) 4-Re-2 (inset spectra are recorded from 204-264 K);
(c) 4-ReAN-3; (d) 4-Re-3.

156
The low temperature spectrum for 4-Re-l is broad and blue-shifted, but the larger
oligomer complexes acquire a highly structured emission with a 615 nm maximum (0,0)
band and 680 nm (0,1) shoulder. Note that this emission maximum is very similar to
the 614 nm phosphorescence maximum observed in the 4-L emission spectra (Figure 5-
3). Also, no overlapping spectral elements are apparent in these spectra, which is quite
different than the 5-Re and 5-ReP spectra (Figures 3-6 and 4-4). A clear transition
between the broad MLCT emission and structured 3n,n* emission can be seen for 4-Re-2
in the Figure 5-4b inset at 240 K. This same transition is not seen in 4-Re-3 and
4-ReAN-3 spectra, where the structure is retained at all temperatures. These observations
suggest that the observed emission in the 4-Re complexes (except 4-Re-l) is 7i,7t*
phosphorescence at low temperature and 3MLCT luminescence (or a mixture of the two
excited states) at room temperature.
To further prove the conclusion that the low-temperature emission is ligand-based
n,n* phosphorescence, excitation polarization studies were conducted on 2-MTHF
solutions at 80 K of 4-Re-3 at various emission wavelengths. Excitation spectra and r(X.)
values are shown in Figure 5-5, along with an emission spectrum that indicates the
studied wavelengths. For all the recorded excitation spectra, the anisotropy value is low
(« 0) and does not vary across the excitation spectrum. The observation of unpolarized
light that is excitation wavelength independent confirms the emission band assignment as
oligomer n,n* phosphorescence, as seen in the 5-Re and 5-ReP polarized excitation
The odd high-temperature emission spectra recorded for 4-Re-3 are due to a significant
4-L-3 impurity in the studied sample.

157
spectra (Figures 3-7 and 4-5). However, the 80 K 4-Re emission spectrum is entirely
phosphorescence, with no evidence of an overlapping MLCT state as seen in the “linear”
oligomer complexes. Furthermore, the anisotropy values are higher for the 5-Re-3 and
5-ReP-3 polarization data (« 0.05), suggesting excited-state mixing in these complexes
that is not observed in the 4-Re-3 polarization data. Surprisingly, polarization
measurements on 4-Re-l returned anisotropy values very similar to those observed for
5-Re-3, with a low value (0.07) that is excitation wavelength independent. This
observation suggests for 4-Re-l that at low temperature a ligand-based phosphorescence
might be mixed with the observed MLCT emission.
The 4-ReAN-3 emission spectra and temperature response are practically identical
to the 4-Re-3 spectra, which is not surprising if the majority of the emission is ligand-
based. The room temperature emission quantum yield, however, decreases dramatically
upon ligand substitution, which is counter to expected results for acetonitrile-substituted
complexes. These observations, which are very similar to those observed for 5-ReAN-2
and 5-ReAN-3, suggest that ligand substitution alters the excited-state equilibria for the
4-Re complexes to a similar degree as that observed for the 5-Re complexes (Figure
3-17).
Emission Lifetimes
Emission lifetime decays were recorded for two different emission wavelengths
on the 4-L oligomers in 2-MTHF at room temperature and 80 K. Both monoexponential
and biexponential decays were observed, and lifetime results are listed in Table 5-3.

158
2
c
(0
k.
*-»
A
t—
<
J
(A
C
0)
<->
_c
c
o
'35
(A
E
LU
0.4
0.3
0.2
0.1
0.0
0.4
0.3
0.2
0.1
0.0
0.4
0.3
0.2
0.1
0.0
300 350 400 450 500 550
Wavelength / nm
Figure 5-5: Excitation (dashed line) and excitation polarization (solid line) r(A.) spectra at
80 K of 4-Re-3 2-MTHF solution at various emission wavelengths.

159
Table 5-3: Variable temperature emission decay times of the 4-L oligomers.
Oligomer3
T/K
OCi
450 nm Emission
Xi / ns (X2
x2 / ns
a.
600 nm Emission
Xi / ns a2
x2 / ns
4-L-l
298
1
1.317
-
-
0.995
1.573
0.005
46.82
80
0.989
1.275
0.011
12.28
1
84100
-
-
4-L-2
298
1
1.461
-
-
0.986
1.374
0.014
8.167
80
0.889
0.909
0.111
2.184
1
153000
-
-
4-L-3
298
1
1.153
-
-
-
-
-
-
80
0.903
0.887
0.097
1.897
0.946
1.691
0.054
9.407
a2-MTHF solutions; 405 nm excitation. Biexponential decays were modeled based on (3-3). Errors for the
fit parameters are ± 5%.
Fluorescence emission lifetimes (450 nm) are short at room temperature (around 1
ns) and become biexponential at low temperature with the addition of a low amplitude,
longer lived (7 ns) component. This photophysical behavior is identical to the “excimer-
like” behavior observed in the 5-L and 5-LP oligomers (Tables 3-3 and 4-3), again
confirming the presence of aggregation in the 4-L oligomers. The phosphorescence (600
nm) observed in 4-L-l and 4-L-2 exhibited monoexponential decay with a very long
lifetime (> 80 ps) at 80 K, which is typical for organic phosphorescence.108
Emission decay lifetimes were recorded for the 4-Re complexes in 2-MTHF at
various temperatures. Biexponential decays were observed at all temperatures, and
results are listed in Table 5-4. At room temperature, the emission decays are
biexponential and characterized by a large amplitude, short-lived component (x = 1 ns)
and a low-amplitude component with a longer lifetime (x = 50 - 150 ns). In contrast, at
reduced temperatures the long-lifetime component dramatically increases in both
amplitude and lifetime (x > 40 ps). These observations reflect the domination of

160
phosphorescence in the low-temperature emission spectra. However, the presence of a
biexponential decay still signifies an excited state equilibrium similar to that previously
described for the 5-Re and 5-ReP complexes. This equilibrium results in a
phosphorescence lifetime that is shorter than those recorded for 4-L-l and 4-L-2 under
the same degassing conditions. Alternatively, a small free oligomer impurity could result
in the biexponential behavior.
Table 5-4: Variable temperature emission decay times of the 4-Re complexes.
Complex2
Temp. / K
Ti / ns
a2
x2 / ns
4-Re-l
298
0.824
1.604
0.176
47.99
171
0.723
155.77
0.277
626.2
90
0.588
1286.7
0.412
3734.5
4-Re-2
298
0.928
1.931
0.072
151.8
180
0.968
10.00
0.032
16485
91
0.870
10.35
0.130
49222
4-Re-3
298
0.954
1.025
0.046
168.74
181
0.984
5.832
0.016
14489
85
0.948
6.235
0.052
34565
4-ReAN-3
298
0.935
8.289
0.065
4461
169
0.992
0.860
0.008
159.8
80
0.965
1.720
0.035
385.3
“2-MTHF solutions, 350 or 405 nm Excitation. Decays were recorded at 600 nm. Biexponential decays
were modeled based on (3-3). Errors for the fit parameters are ± 5%.
Note the decreasing phosphorescence decay amplitude with increasing oligomer
size. The trend is similar to the 4-L oligomer phosphorescence, which decreases in
efficiency with increasing oligomer size due to the increasing availability of a competing
nonradiative pathway. The 4-ReAN-3 low temperature emission lifetimes are nearly two

161
orders of magnitude smaller than 4-Re-3. This trend is the opposite of what is expected
for the acetonitrile-substituted chromophore, which should increase the emission lifetime.
This trend further supports an excited-state equilibrium in the 4-Re complexes.
Furthermore, the longer room temperature lifetime for 4-ReAN-3 compared to 5-ReAN-2
and 5-ReAN-3 illustrates the influence of the 71,71* phosphorescence on the “bent”
oligomer complex emission.
Transient Absorption Spectra
Transient absorption spectra for the 4-L oligomers in THF solutions are shown in
Figure 5-6. Excited state lifetimes obtained from factor analysis and global decay
fitting114 are listed in Table 5-1. Equivalent first order decays were observed for all
features of the various transient absorption spectra.
The spectra show bleaching of the lowest energy 71,71* ground state absorption
(Figure 5-2) at 400 nm and a broad long-lived excited-state absorption. The excited state
lifetimes are all very long and similar to the phosphorescence lifetimes obtained for 4-L-l
and 4-L-2. The transient absorption spectra for the 4-L oligomers are very similar to the
5-L and 5-LP spectra (Figures 3-8 and 4-6) except that the absorption maximum is blue-
shifted by 50 nm. It is interesting to note that 4-L-l exhibits excited-state absorptions
that do not correspond with the larger oligomer spectra. In fact, the prominent 390 nm
transient is more similar to a bipyridine radical anion transient absorption.153 This
difference may be due to the lack of extended conjugation in 4-L-l, which may give rise
to higher-energy excited state transitions similar to 2,2’-bipyridine.

162
0.020
0.015
(1)
o
c
re
n
k_
o
(A
n
<
400 500 600 700 800
Wavelength / nm
Figure 5-6: Transient absorption spectra of the 4-L oligomers in freeze-pump-thaw
degassed THF solutions. Arrows indicate the spectral trend with increasing time after
laser excitation, (a) 4-L-l (Transients are 40 ps increments after laser excitation);
(b) 4-L-2 (Transients are 40 ps increments after laser excitation); (c) 4-L-3 (Transients
are 80 ps increments after laser excitation).

163
Transient absorption spectra of the 4-Re complexes in THF solutions are shown
in Figure 5-7. Excited state lifetimes obtained from factor analysis and global decay
fitting114 are listed in Table 5-2. Spectra were recorded in CH2CI2 for 4-ReAN-3 to
prevent photosubstitution of the CH3CN ligand. Generally, equivalent first order decays
were observed for all features of the various transient absorption spectra. However, the
450 nm bleach transient exhibited biexponential decay in certain samples with a rapid (x
< 1 ns) component followed by a slower decay lifetime that corresponded to the other
decay lifetimes in the transient absorption spectrum. This result is due to trace 4-L
oligomer impurities in the examined samples and is similar to behavior observed for the
5-Re and 5-ReP complexes discussed in previous chapters.
Ground state bleaching is observed similar to the 4-L spectra but red-shifted to
reflect the red-shifted ground state 7t,7t* absorption. A broad excited-state absorption is
also observed with maxima around 520 nm for 4-Re-l and 650 nm for 4-Re-2 and
4-Re-3. The excited-state absorptions are very similar for the 4-L oligomers and the
4-Re-2 and 4-Re-3 complexes, suggesting that they all originate from similar n,n*
excited states. The 4-Re-l spectrum, however, with its 350 and 520 nm absorptions is
more similar to (bipyridine)Re‘(CO)3Cl spectra and 4-L-l, suggesting that the 4,4’-
substitutions do not exert a significant effect on the excited state behavior until
4-Re-2.94,154 The transient decay lifetime for the 4-Re complexes (except 4-ReAN-3) is
much shorter than the 4-L oligomers and very similar to the observed emission decay
long-lifetime component, suggesting that an excited-state equilibrium exists to cause the
similar lifetimes originating from different excited-states. For 4-ReAN-3, a longer
transient lifetime was observed, exhibiting the same trend seen in 5-ReAN-2 and

164
5-ReAN-3 and confirming an excited-state equilibrium disruption in the acetonitrile-
substituted complexes.
Figure 5-7: Transient absorption spectra of the 4-Re rhenium complexes in argon
bubble-degassed THF solutions (except 4-ReAN-3, which is in CH2CI2). Arrows show
the spectral trend with increasing time after laser excitation, (a) 4-Re-l (Transients are
40 ns increments after laser excitation); (b) 4-Re-2 (Transients are 80 ns increments after
laser excitation); (c) 4-Re-3 (Transients are 80 ns increments after laser excitation); (d)
4-ReAN-3 (Transients are 4000 ns increments after laser excitation).

165
Photothermal Measurements / Triplet Yields
LIO AS measurements were performed on THF solutions of the 4-L oligomers and
4-Re complexes with the 5 MHz transducer. For the 4-L oligomers, a single fast
component was observed, resulting in a single amplitude with an insignificant lifetime.
Results of multiple 4-L oligomer measurements are listed in Table 5-5. For the 4-Re
complexes, two components (one fast and one intermediate lifetime) were observed.
Measurements of 4-Re-l are impractical due to its short excited state lifetime. Results of
multiple 4-Re complex measurements are listed in Table 5-6.
Table 5-5: 4-L oligomer LIO AS data.
Oligomer3
i
4-L-l
0.2743 ± 0.02
4-L-2
0.2934 ± 0.03
4-L-3
0.3105 ±0.02
“THF solutions, 298 K. LIOAS
deconvolution parameters are
averages of four measurements
on fresh sample solutions with a
reported error of ± a. X! fixed at
1 ns.
Table 5-6: 4-Re complex LIOAS data.
Complex3
i
2
x2 / ns
4-Re-2
0.3564 ± 0.020
0.5719 ±0.054
129.8 ±3.76
4-Re-3
0.4793 ± 0.030
0.4056 ± 0.025
196.4 ± 10.6
aTHF solutions, 298 K. LIOAS deconvolution parameters are
averages of four measurements on fresh sample solutions with a
reported error of ± a. x, fixed at 1 ns.

166
The LIOAS data measured on the 4-L oligomers and 4-Re complexes can be used
to calculate the excited-state triplet yields. The 4-L-l and 4-L-2 phosphorescence
provides the triplet energy needed for the triplet yield calculation (614 nm = 46.6 kcal
mol’1) if the assumption is made that the triplet energy does not vary across the oligomer
series. The triplet yields can subsequently be calculated using (3-6) as before, and the
results are listed in Table 5-7. Recall that for 4-L-2 and 4-L-3 emission quantum yields
were very difficult to accurately measure, and the numbers reported in Table 5-1 give
erroneous results in this calculation. Therefore, the emission quantum yield for these
oligomers was assumed to be greater than 0.7, producing the reported “upper bound”
triplet yields.
Table 5-7: 4-L oligomer triplet yields.
Oligomer8
T
4-L-l
0.12
4-L-2
<, 0.20
4-L-3
<0.18
aTHF solutions, 298 K. Errors
for the triplet yield are ±15%.
The 4-Re-2 and 4-Re-3 triplet yields can also be calculated from the LIOAS data
by assuming the same triplet energy used for the 4-L data. Recall that the transient
absorption spectra for both the 4-L oligomers and 4-Re complexes are similar, suggesting
that the same excited state (oligomer 37r,7i*) is populated in both cases. Therefore, this
excited state is the lowest-energy excited state that would be responsible for the

167
deconvolution component. The triplet yield can then be calculated by independently
using each decay component in (5-1).
Ehu
i =â– 
'hu
2 -
<|>TET(l (|)em)
'hu
Calculated 4-Re-2 and 4-Re-3 triplet yields are listed in Table 5-8.
Table 5-8: Triplet photophysics of the 4-Re complexes.
Complex8
<))Tb
4>tc
4-Re-2
* 1.00
0.99
4-Re-3
H't’t tt"' i ■ ; _ n
0.90
0.70
deconvolution amplitude (5-la). ‘Triplet yield based on
the second deconvolution amplitude (5-lb).
(5-la)
(5-lb)
It is clear from the calculations that the triplet yields are much higher in the 4-Re
complexes than the 4-L oligomers. While intersystem crossing yields for rhenium
complexes are commonly close to unity,76 the data in this case are indicative that the
triplet yield is enhanced by the presence of the metal chromophore (i.e., the 3MLCT
excited state serves as a conduit for 3n,7i* excited state formation). The triplet yield
decrease observed for 4-Re-3 is surprising but likely originates from errors in the triplet
yield measurements.
Decay Rate Calculations
Sufficient data is now available to calculate the radiative, intersystem crossing,
and nonradiative decay rate constants for the 4-L oligomers based on (3-6). The Srickler-

168
Berg equation (3-7) can also be used to calculate the radiative rate constant in a similar
manner to the 5-L oligomer calculations. The experimental and calculation results are
listed in Table 5-9. Note that for 4-L-2 and 4-L-3 limits are given for the rate constants
due to the emission quantum yield assumption used in the LIOAS calculations.
Table 5-9: Decay rates of the 4-L oligomers.
Oligomer
kr/10V
k„r /107 s'1
k¡sc /107 s'
krSB /108 s'1
4-L-l
6.35
9.07
9.89
0.978
4-L-2
>4.79
<6.84
< 13.7
4.17
4-L-3
>6.07
< 10.4
< 15.6
4.12
Several observations stem from this data. Of course, the limitations of drawing
any decisive conclusions from these numbers are obvious since exact values are not
obtained for 4-L-2 and 4-L-3. First, note that kr does not increase with increasing
oligomer size as readily as observed with the 5-L oligomers (Table 3-10). This trend
suggests a marked difference in the ability of the “bent” oligomer extended n-conjugation
to influence its excited-state photophysics. Second, the calculated krSB values still agree
with the experimental values (except for 4-L-l), suggesting that the fluorescence
originates from the lowest-energy absorption band and is strongly allowed. Third, the knr
values are larger for the 4-L oligomers than the 5-L oligomers, while the k¡sc values are
smaller. Since it is likely that radiative and intersystem crossing pathways are the major
deactivation pathways of the '71,71* state (i.e., em + isc« 1), the actual knr values are
certainly much lower than the upper bounds reported here.

169
Electrochemistry
Cyclic voltammetry was performed on the 4-Re complexes in THF with 0.1 M
TBAH as the supporting electrolyte. Again, the limited THF potential window prevented
the measurement of oxidation potentials. Quasi-reversible reduction waves of the organic
oligomer were observed in all cases, and half-wave potentials are listed in Table 5-1. The
reduction potential (and, subsequently, excited state energy) does not change much as the
oligomer size increases. The potentials are slightly more negative than the 5-Re
complexes (Table 3-1), suggesting that the PPE-type oligomer is harder to reduce when
the aryl-ethynyl moieties are substituents at the 4,4’ positions on the ligated bipyridine.
Electroabsorption Spectroscopy
In order to investigate the differences between the transition dipoles associated
with the ligand n,n* and metal MLCT transitions, electroabsorption spectroscopy (also
known as stark effect spectroscopy) was employed in a collaboration with Dr. Linda
Peteanu and Lavanya Premvardhan at Carnegie Mellon University. This technique has
been used to investigate dipole moment changes associated with MLCT transitions in
ruthenium complexes with a high degree of success.155'158 Electroabsorption
spectroscopy involves monitoring the ground-state absorption spectrum change as the
sample is subjected to a rapidly oscillating electric field. The resulting field-induced
effects are modeled as a combination of the zeroth, first, and second derivatives of the
original absorption spectrum to allow the extraction of information on the transition
dipole moment and polarizability changes associated with the optical transition. The fit
equations are specified in (5-2).155,159

170
(5-2a)
(5-2b)
Cx =|An|2[5 + (3cos2^-l)(3cos25c-l)]
(5-2c)
In (5-2), A(u) is the absorption spectrum, u is the absorption spectrum frequency,
Fint is the internal electric field, TrAa is the trace of the molecular polarizability change,
X is the angle between the electric field and optical axis, g ■ Aa • g is the molecular
polarizability change along the transision moment, Ap is the dipole moment change, and
is the angle between the transition dipole moment and the “change in dipole” moment
(i.e., difference between ground and excited-state dipole moments). To fit
electroabsorption data, the original absorption spectrum is modeled with combinations of
Gaussian peaks that best reproduce the data and mathematically separate the different
transitions of interest. After taking the zeroth, first, and second derivatives of the model,
(5-2a) is used to yield the best fits for parameters Ax,t Bx, and Cx. If data is acquired for
two different x values (typically 0° and 54.7°), the dipole moment and polarizability
changes can readily be extracted for the various components of the absorption
spectrum.155
The 4-Re-l complex was selected for these experiments since it is the only
complex that exhibited an MLCT absorption shoulder not completely obscured by the
t Note that Ax contains information regarding transition moment polarizability and is
usually zero for MLCT electroabsorption measurements, so it is not considered here.

171
more intense 7r,7i* absorptions. Electroabsorption spectroscopy for 4-Re-l in a
polymethylmethacrylate (PMMA) matrix at 77 K is shown in Figure 5-8. Although three
Gaussians were needed to properly model the absorption spectrum, the electroabsorption
response is fit to a sum of only Gaussians 1 and 3 as shown in Figure 5-8a. The use of
Gaussian functions to model the two observed absorption bands in the 4-Re-l spectrum
(Figure 5-2) allows the expansion of (5-2a) to a six-parameter fit and the extraction of Ap
and Aa values for each transition.159 For the low-energy band, three independent
measurements produced an average Ap of 8.7 ± 0.5 Debye and Aa of 60 Á3, while the
higher-energy band returned an average Ap of 8.0 ± 0.5 Debye and Aa of 31 Á3.
Therefore, within experimental error the two bands have the same Ap value, both at room
temperature and 77 K. These results are similar to those previously reported by Oh and
Boxer158 for Ru(bpy)32+, where the MLCT Ap was 8.8 Debye.
The positive Aa values indicate that the excited state exhibits a greater propensity
for polarization than the ground state, and the higher Aa value for the lower-energy band
is likely a contribution from the overlapping MLCT absorption within the more intense
7i,7i* band. The similar Ap values for both transitions suggest that the two transitions
populate very similar excited states. That is, the n,n* absorption dominates both bands as
previously concluded from the high absorbptivity values. However, the slightly higher
Ap value for the lower-energy transition may result from additional contribution from the
Hupp obtained a Aa of 570 ± 100 Á3 for the MLCT absorption of ruthenium(II)
tris(phenanthroline), which is considerably larger than our results and likely due to the
lack of overlapping organic and metal-based transitions.155

172
overlapping MLCT transition that would constructively interfere with the 7i,7r* transition
Ap.
Figure 5-8: Electroabsorption spectroscopy of 4-Re-l in a PMMA matrix at 80 K. (a)
Absorption spectrum illustrating Gaussians utilized in data fitting; (b) Electroabsorption
signal and fitting results using (5-2) and (Gaussian 1 + 3) as the model.
Discussion
Excited-State Energetics
The 4-Re photophysics requires a slight alteration of the excited-state model
presented for the 5-Re complexes in chapter 3. Therefore, the model illustrated in the
Jablonski diagram shown in Figure 5-9 is proposed.

173
Figure 5-9: Jablonski diagram of 4-Re complexes.
The general construction of this diagram is very similar to that presented for the
5-Re complexes (Figure 3-18), except for a slight raising of the oligomer '71,71* energy, a
slight lowering of the oligomer 37t,7i* energy and the introduction of oligomer
phosphorescence (EMI in Figure 5-9). The same excited-state equilibrium exists
between the oligomer-based 37i,7i* and metal-based 3MLCT states, but the lowered 37t,7t*
energy alters the temperature-dependence of the emission behavior. At room
temperature, the equilibrium results in the observation of 3MLCT emission (EM2 in
Figure 5-9), since the oligomer phosphorescence is superceded by nonradiative decay at
these temperatures. As the temperature is lowered, the thermal energy necessary to
maintain equilibrium between the excited states is no longer present, and the electronic
population collects in the 37r,7t* state. Furthermore, the nonradiative decay pathway

174
favorable at room temperature gradually gives way to phosphorescence, which is the only
emission observed at low temperatures. The biexponential emission decays obtained at
80 K, however, suggest that the 3MLCT excited state still has some small effect on the
decay through the aforementioned equilibrium. Alternatively, an impurity could be
responsible for the fast component of the emission decay.
The transient absorption spectra, due to their similarity to the 5-Re spectra (Figure
3-10), still originate from the oligomer 37t,7t* state (TA in Figure 5-9) following
equilibration. The presence of the acetonitrile ligand in 4-ReAN-3 raises the 3MLCT
energy, disrupting the excited-state equilibrium as before and producing the shortened
emission and increased TA room temperature lifetimes. No changes are observed in the
emission and TA spectral bandshapes upon acetonitrile substitution, however, since the
oligomer is responsible for the observed spectra.
How Does the Substitution Position Alter the Photophysics?
As illustrated above, there are subtle differences between the photophysics of the
“linear” and “bent” oligomers and rhenium complexes. Namely, the excited-state singlet
energy is higher while the triplet energy is slightly lower for the “bent” oligomers with
respect to the “linear” systems. In order to better understand these differences, literature
precedents were investigated to see if similar substitution trends have been observed.
Extensive photophysics have been conducted on stilbazoles (styrylpyridines), both by
themselves and incorporated into -Re(CO)3Cl chromophores (Figure 5-10). Some of
these results are considered here for comparison to our systems. Note that 3-SA
structurally corresponds to the 5-L and 5-LP oligomers while 4-SA structurally
corresponds to the 4-L oligomers.

175
Re-3-SA: Re'(CO)3CI(3-SA)2
Re-4-SA: Re'(CO)3CI(4-SA)2
Figure 5-10: Stilbazole-containing complexes.
Photophysics of 2-SA, 3-SA and 4-SA were studied by Bartocci160 and Gómer,161
and fluorescence quantum yields and triplet energies are listed in Table 5-10.
Table 5-10: 2-SA, 3-SA and 4-SA photophysical data (Ref. 160-161).
Molecule
On
Et / kcal mol'1
2-SA
0.002
49.0
3-SA
0.065
48.8
4-SA
0.003
49.2
Note that the triplet energy remains constant, but 3-SA is more emissive by an order of
magnitude. The major excited-state deactivation pathway for stilbazoles is
photoisomerization, but for 3-SA this capability is clearly hampered. Bartocci and

176
coworkers explain this difference based upon the heteroatom position, which significantly
alters the excited state molecular orbital nodal structure and inhibits the internal
conversion needed to induce photoisomerization.160 The 2-SA and 4-SA equivalency
illustrates the lack of a node at these atom positions. While the stilbazole photochemistry
is different than our PPE-type oligomers, the idea that heteroatom positioning affects the
excited-state photophysics is highly relevant. Note that the increased (j)em for the 4-L
oligomers is the opposite observed for the stilbazoles, where 3-SA has a higher
fluorescence quantum yield.
Wrighton and coworkers162 synthesized rhenium complexes Re-3-SA and
Re-4-SA as part of a photoassisted reactions study. While they did not embark on
detailed photophysical studies, an interesting trend was observed. First, the lowest-
energy absorption (associated with the 71,71* transition of the styrylpyridine ligands) is 30
nm blue-shifted for Re-3-SA (297 nm) compared to Re-4-SA (328 nm). Note that this
trend is opposite that observed for the 5-Re and 4-Re complexes, where the 4-Re
complexes have higher-energy absorptions. Of course, stilbazole complexes might not be
the best model for these oligomers since they lack the rigidity of the acetylene linkages
(i.e., no possibility of photoisomerization) and a bipyridine moiety.
One additional study by Zhou and Swager16 examined the photophysics of
“linear” and “bent” PPE-type polymers SP1 and SP2, as shown in Figure 5-11.
Absorption measurements on these polymers showed that SP2 (388 nm) is blue-shifted
with respect to SP1 (428 nm), agreeing with the 5-L / 4-L spectral trends. This
observation shows that the “bent” polymer excited states are higher in energy than the
“linear” polymer due to the different structure. While the authors did not speculate why

177
the excited state energies change, it clearly is due to the differing polymer substitutional
geometry,
CON(C8H17)2.OC10H2i
H-p—-■pH
(C8H17)2NOC C10H2iO
SP1 SP2
Figure 5-11: “Linear” and “bent” PPE-type polymers. (Ref. 16)
Semi-Empirical Calculations
In order to better understand the trends observed between the “linear” and “bent”
oligomers, semi-emperical calculations were performed on 4-arylethynylpyridine (4-M)
and 5-arylethynylpyridine (5-M) with Hyperchem and the PM3 / ZINDO basis sets, as
shown in Figure 5-12. The molecular axis was oriented such that the planar molecule
rests in the xy plane, with the y axis corresponding to the long molecular axis. Calculated
excited-state energies and spectroscopic parametersíí are listed in Table 5-11.
tt Of course, the differing phenyl ring substituents might contribute to the observed
absorptions. However, the electron-withdrawing amide substituents on SP1 would draw
electron density from the polymer backbone and blue-shift the absorption,5 which is
counter to the reported observations.
tí Note that the absorption transitions calculated by Hyperchem indicate a single
molecular orbital for the responsible ground and excited-states. This is a simplification
of the configurational interaction output internally performed by the software, as several
different molecular orbitals are mixed in this method to arrive at the electronic transition.
Nevertheless, the simplification is reported here.

178
4-M
5-M
Figure 5-12: Arylethynylpyridine model compounds.
Table 5-11: Semi-empirical calculations for 5-M and 4-M
Parameter3
5-M
4-M
Es / kcal mol'1
105.6
106.4
Et / kcal mol'1
71.1
71.7
Dipole moment / Debye
3.09
3.78
Absorption
N/A
238
(HOMO - 1 -> LUMO) / nm
Absorption
272
268
(HOMO -> LUMO) / nm
Absorption
245
N/A
(HOMO -> LUMO + 1) / nm
“Parameters obtained from ZINDO/CI single point calculations following PM3 geometry optimizations as
described in the experimental section.
For both molecules, two major absorption bands were obtained, corresponding to
the two major 7t,tt* absorptions observed in all PPE-type oligomer reported spectra. The
5-M molecule exhibited slightly lower excited-state energies, reflected in the red-shifted
absorption bands. Molecular orbital diagrams for the states involved in the absorption
bands are shown in Table 5-13. Particular attention is paid to the energy of the molecular

179
orbital that represents the non-bonding electrons on the nitrogen atom (i.e., the molecular
orbital with significant N px character). For 5-M, the highest energy non-bonding
molecular orbital is number 21 A’, with an energy of-14.46 eV and N px coefficient of
+0.263. The 4-M molecule, however has non-bonding molecular orbital 15 Al, with an
energy of -10.06 eV and N px coefficient of +0.377. Therefore, the 4-M non-bonding
molecular orbital is 4 eV closer to the HOMO molecular orbital energy than 5-M (2.01
eV versus 6.70 eV). This observation suggests that the 4-M HOMO -> LUMO transition
exhibits more (n —> 7i*) character than 5-M, which is a (n -» n*) transition. Transitions
involving an isolated non-bonding orbital are typically higher in energy than those
involving a delocalized 7i cloud, and this trend is reflected in the model molecules.
Another interesting trend observed in the calculations is the ratio of oscillator
strengths of the two primary absorptions, which is larger for 5-M (6.73) than 4-M (3.84).
This trend is reflected in the experimental absorption spectra, where the absorption bands
in the 4-L spectra are more equivalent in intensity than the analogous 5-L spectra
(Figures 3-2 and 5-2).
Following the model calculations, the larger 5-L-l and 4-L-l molecules were
considered using the same procedure. Both planar and “twisted” (e.g., the outlying
phenyl rings are rotated 90° to the central bipyridine) versions (5-L-IT and 4-L-IT) of
the oligomers were studied. The molecular axis was configured such that the planar
oligomer is in the xy plane, with the y axis corresponding to the long “oligomer” axis.
Observed and calculated excited-state energies and absorption maxima of the most
intense bands are compared in Table 5-12.

180
Table 5-12: Semi-empirical calculations for 5-L-l and 4-L-l
Parameter®
5-L-l
4-L-l
5-L-1T
4-L-1T
Es / kcal mol'1
81.1
97.0
87.6
104.5
(62.9)
(68.9)
Et / kcal mol'1
61.9
69.1
60.7
71.6
(52.3)
(46.6)
Dipole moment / Debye
4.98
6.27
5.14
6.18
Absorption
N/A
N/A
N/A
268
(HOMO-2 -> LUMO) / nm
Absorption
N/A
274
N/A
N/A
(HOMO - 1 -â–º LUMO) / nm
(296)
Absorption
342
286
317
N/A
(HOMO -â–º LUMO) / nm
(370)
(346)
Absorption
258
N/A
N/A
256
(HOMO -> LUMO + 2) / nm
(330)
“Parameters obtained from ZINDO/CI single point calculations following PM3 geometry optimizations as
described in the experimental section. Experimental values are shown in parenthesis following the
calculated values.
When examining the calculation results, keep in mind that semi-empirical
calculations typically return energies that are erroneously high, presumably due to
overestimation of electron-electron repulsion for the Es values. Several trends are
apparent from this data. First, the calculated Es value is higher for 4-L-l by 16 kcal mol'1
compared to 5-L-l, which is greater than the experimental energy difference but reflects
the correct trend. Second, the calculated Et values exhibit the same trend but with a
smaller increase, which is counter to the experimental trend. Third, the calculated
spectroscopic maxima are all higher in energy than experimental values but exhibit blue-
shifted absorption bands for 4-L-l compared to 5-L-l. Finally, the “twisted” oligomers
exhibit increased Es and absorption maxima energies compared to the coplanar
geometries, while the ET values do not significantly change. This observation supports

181
the argument that breaking the extended conjugation of the oligomer n-backbone can
exhibit significant effects on its excited-state photophysics.
Diagrams illustrating molecular orbitals of interest for the planar and twisted
oligomers are shown in Tables 5-14 and 5-15, respectively. The molecular orbitals
illustrate some interesting trends. For 4-L-l, the HOMO and HOMO - 1 orbitals are very
close in energy (< 0.01 eV) and exhibit delocalization across the entire oligomer with the
molecular orbitals both in and out of phase across the central bipyridine. The LUMO is
also delocalized across the entire oligomer. For 5-L-l, delocalization is exhibited across
the entire oligomer for each molecular orbital. Further investigation of the ZINDO output
uncovers the molecular orbitals associated with the bipyridine nitrogen non-bonding
electrons. For 5-L-l, this orbital is 24 Al, with an energy of-10.25 eV and nitrogen px
coefficients of +0.395 and +0.392 for the two atoms, while the corresponding 4-L-l
molecular orbital is 81 A, with an energy of-9.80 eV and coefficients of +0.249 and
+0.471. The energy differences between these non-bonding molecular orbitals and the
HOMO are 3.1 and 1.97 eV for 5-L-l and 4-L-l, respectively. Therefore, these energy
differences suggest that the HOMO -> LUMO transition exhibits more (n —» n*)
character in 4-L-l than 5-L-l, which would result in the observed absorption blue-shift
and follows the trend observed in 4-M and 5-M above.
The twisted oligomer molecular orbitals support previous suggestions that
electronic isolation occurs due to conjugation breaks in the oligomer backbone. For
5-L-1T, the HOMO and LUMO orbitals are isolated to the central bipyridine. The
4-L-1T absorption transitions stem from molecular orbitals isolated on the central
bipyridine (HOMO - 2 and LUMO) and one of the peripheral segments (HOMO - 1 and

182
LUMO + 1), both of which are higher in energy than the planar 4-L-l transitions.§§
These calculations confirm the possibility of having electronically isolated chromophores
within the same oligomer, which can account for some of the photophysical behavior
exhibited in previous chapters (e.g., the presence of oligomer and complex absorptions in
5-Re-4).
The semi-empirical calculations presented here shed some light on the differing
photophysics of the two oligomer series. Clearly, the wavefunctions for the 4,4’-
substituted bipyridine are dramatically altered by the geometry change, presumably by the
position of the nitrogen atoms relative to the peripheral conjugated arms of the oligomer,
which alters the relative energy of the molecular orbitals corresponding to the nitrogen
non-bonding electrons. Furthermore, the nature of the electronic transition appears to
change between the two oligomer geometries, as the 4-Re oligomers exhibit more (n -»
7i*) character. It is interesting that no other literature precedents for substitution effects
exhibit the same trends found here, but the large bulk of our “substitutions” must be kept
in mind when making literature comparisons.
Mulliken Theory Calculation of 4-Re-l MLCT Dipole Moment
To further support the electroabsorption measurements of Ap, calculations based
on Mulliken theory were performed to determine the MLCT transition moment, pDA,
based on (5-3).163'165
M^DA =-e^ad^aa (5‘3a)
§§ Some of the odd behavior of the 4-Re-lT calculations may stem from the inability to
design a symmetric molecule in the Hyperchem editor.

183
*1-=-^- (5-3b)
^MLCT
Raa = ZCjaZj + Z Z CjaCkaSjk (Zj + Zk ) (5-3c)
j j k
(j In (5-3), e is the charge of an electron (-1.60 x 10'19 C), A.ad is the donor-acceptor
mixing coefficient, pad is the off-diagonal interaction energy of the donor (Re dyz) and
acceptor (N py) orbitals, Emlct is the charge transfer energy, Cja is the LUMO 7i*
molecular orbital py orbital coefficient of atom j, Zj is the z-axis distance from the
rhenium atom center to atom j, and Sjk is the overlap integral of the py orbitals on atoms j
and k. All non-hydrogen atoms in the acceptor orbital ligand are considered when
calculating Raa. The parameters needed for pad, Sjk, and Cja were determined by an
Extended Hiickel calculation performed with Hyperchem 5.0 on 4-Re-l. The 4-Re-l
model was built with a planar oligomer geometry and octahedral rhenium center, with the
oligomer contained in the xz plane, the z axis running along the oligomer center of
symmetry, and the rhenium center at the origin. The LUMO molecular orbital obtained
from the calculation is shown in Figure 5-13.
Using (5-3c), the calculated Raa value for 4-Re-l is 2.53 Á, and the pad value
extracted from the program output is -1.66 eV. This interaction energy, when considered
with an Emlct value of 2.76 eV (based on the assumption that the 4-Re-l MLCT
absorption is 450 nm), gives a Xad value of 0.60. This mixing coefficient is slightly high
for MLCT transitions (0.25 - 0.50), which is probably a symptom of the extended n
delocalization in the complexed oligomer. Final calculation of pDA with (5-3a) yields a
value of 7.30 Debye, which is very close to the Ap values measured by electroabsorption

184
spectroscopy (8.0 and 8.7 Debye for the two n,n* transitions). It is intriguing that the
calculated dipole moment for the MLCT transition is closer to the experimentally-
determined n,n* dipole moments than expected, which might suggest that a larger
fraction of the low-energy absorption is actually MLCT-based than previously concluded.
Figure 5-13: 4-Re-l calculated LUMO molecular orbital.
Mulliken theory can be taken a step further to determine the molar absorptivity
values of the charge transfer transition based on (5-4).
oav Je(u)do = KC^aS^eNR^ (5-4)
In (5-4), uav is the average transition energy, e(u) is the molar absorptivity at frequency u,
K is an experimental constant, Cn3 is the LUMO molecular orbital coefficient of the
nitrogen py orbitals, and Srcn is the overlap integral between the nitrogen py and rhenium
dyz atomic orbitals. In order to determine K, similar calculations were performed on
(4,4’-dimethyl-2,2’-bipyridine)rhenium(I)triscarbonyl chloride, which has known molar
absorptivity values.41 Extended Hiickel calculations on a model placed on the same
molecular axis used for 4-Re-l produced the following parameters: R¡¡ = 1.445 Á, p =

185
1.67 eV, Emlct = 3.41 eV, A,ad = 0.49, pda = 3.40 Debye, Cn3 = -0.2986, and Srcn =
-0.0735. An absorption spectrum of the rhenium model, where only the MLCT
absorption band is integrated, yields a oav Js(u)du value of 4.79 x 1032 M'1 cm’1 s'2.
Substituting all the appropriate values into (5-4) results in a K value of 4.758 x 1051 M'1
cm'3 s'2.
If we use the empirically-derived K value in (5-4) with the 4-Re-l parameters
(CNa = -0.31162, SReN = -0.0723, and R¡¡ = 2.533 Á), a uav Js(u)du value of 1.50 x 1033
M'1 cm'1 s'2 is obtained. This value is roughly half the experimental value of 3.28 x 1033
M' cm' s' , which further supports the conclusion that the low-energy absorption band
has a higher contribution from an MLCT transition than previously believed. While it is
difficult to assign the band as entirely MLCT in nature due to its high absorptivity values,
these calculations suggest that the MLCT transition is not merely being covered up by the
oligomer-based n,n* transition. Rather, the MLCT transition is mixed with the n,n*
transition to such a degree that it exerts a significant effect on the observed absorption
band.

Table 5-13: Singlet ground state molecular orbitals for 5-M and 4-M.
Molecular 5-M
Orbital8
HOMO-1
4-M
KÍ
>
to
i
v©
n>
<
o»
co
oo
©
o»
a>
<
Os
oo
©
u>
L/l
5-M : R, = N, R2 = CH
4-M : R, = CH, R2 = N
oo
Os
“Parameters obtained from ZINDO/CI single point calculations following PM3 geometry optimizations as described in the experimental
section. The pyridine is the aromatic ring on the right side of the molecule as indicated.

Table 5-14: Singlet ground state molecular orbitals for 5-L-l and 4-L-l.
Molecular 5-L-l
Orbital3
HOMO- 1
00
OO
>
l
-4
oo
a
<
HOMO
6
L/t

<
LUMO
o
W
i
o
Os
so
a>
<
LUMO + 2
co
¿
o
n>
<
oo
>
^4
OO
U)
a>
<
o
>
I
o
b\
o
a>
<
4-L-l
oo
Parameters obtained from ZINDO/CI single point calculations following PM3 geometry optimizations as described in the experimental
section.

Table 5-15: Singlet ground state molecular orbitals for 5-L-1T and 4-L-1T.
Molecular
Orbital"
HOMO-2
5-L-1T
00
-o
>
00
k>
-J

<
HOMO
LUMO + 2
ho
>
to
o
n
<
4-L-1T
oo
oo
"Parameters obtained from ZINDO/CI single point calculations following PM3 geometry optimizations as described in the experimental
section.

189
Experimental
Oligomer and Complex Synthesis
The 4-L oligomers and 4-Re complexes were previously synthesized, and their
synthesis is described in detail elsewhere."
4-ReAN-3. 4-Re-3 (18 mg, 7.47 pmol) was dissolved in 20 mL methylene
chloride, whereupon 6 mL of CH3CN and AgOTf (20 mg, excess) was added. The
solution was stirred at room temperature overnight. A TLC (1:1 hexanesiCL^Ch) on
silica showed two spots, Rf = 1 (4-ReAN-3) and Rf = 0.5 (4-Re-3). Additional stirring
and addition of CH3CN produced the final product. AgCl was removed from the sample
solution by filtration on a medium-porosity glass frit through celite, and the filtrate was
reduced by rotary evaporation to produce the final product as a triflate salt. Due to the
small amount of material available, further purification was impractical. IR (THF soln,
cm'1), 1966, 2097, 2134 (oc=o), 2281 (uCsN). ESI-MS caled for C,5iHi98N30,iRe: 2411;
found: 2372 (parent - CH3CN).
Photophysical Measurements
All sample solutions studied were in either THF, 2-methyltetrahydrofuran (2-
MTHF), or CH2CI2. All solvents were distilled according to typical laboratory practices.
All photophysical studies were conducted with the same instrumentation and techniques
described in chapter 3.
Electroabsorption spectra were recorded on PMMA films doped with 4-Re-l at
room temperature and 77 K on an in-house apparatus. An Oriel 150 W xenon arc lamp
coupled to a Spex monochromator and polarizer provided horizontally polarized

190
excitation light. A Joe Rolfe high-voltage AC power supply was used to apply a field of
approximately 3.0 kV at 440 Hz to the thin film sample. Transmitted light was detected
with a silicon photodiode, and the electroabsorption response was extracted from the
signal with a Stanford Research Systems 850 lock-in amplifier.1'9 Three measurements
at each temperature were recorded on two different polymer samples, and each
experiment returned nearly identical results, confirming their validity.
Electrochemical Measurements
All electrochemical measurements were conducted on THF solutions with TBAH
as the supporting electrolyte. Cyclic voltammetry measurements were performed with the
same procedures and the same instrumentation described in chapter 3.
Semi-Empirical Calculations
All calculations were performed with Hyperchem version 5.0.166 4-L-l and 5-L-l
models were built within the program editor with an initial planar geometry. Polak-
Ribiere geometry optimizations were performed with successive UHF/PM3 calculations
and no imposed molecular restraints. All molecules retained an essentially planar form (<
2° torsion) after optimization. Finally, a single-point RHF/ZINDOs Cl calculation was
performed to obtain the final energies, spectroscopic parameters and molecular orbitals.
A single-point Extended Hiickel calculation was performed on the 4-Re-l model
described above with a K factor of 1.75, and relevant information was extracted from the
program output file.

THIOPHENE PHOTOPHYSICS
Introduction
In a collaborative research effort with Dr. Stephan Guillerez and Lise Trouillet at
CEA-Grenoble, the photophysics of MLCT-incorporated rr-conjugated polymers with a
poly-3-alkylthiophene backbone were studied. The group in Grenoble has been involved
in synthesizing regiospecific (HT-HT) polythiophenes with integrated 2,2’-bipyridine
subunits spaced after every four or six thiophene rings that serve as inorganic MLCT
chromophore coordination sites.37,167,168 The focus of the investigation is on the
properties of organic polymer P4 (Mn =111 kg mole'1, Mw = 244 kg mole'1, PDI = 2.20)
and the three metal-organic polymers, P4-Ru (Mn = 29 kg mole'1, Mw = 70 kg mole"1,
PDI = 2.41), P6-Ru and P4-Os (Figure 6-1). Each of these polymers contains a repeat
unit structure consisting of a tris-bipyridine Ru(II) or Os(II) complex flanked by a
regioregular 3-octylthiophene tetramer or hexamer. Both -Ru(bpy)32+ and -Os(bpy)32+
chromophores were integrated into the polymers due to the inherent differing electronic
structure of these two chromophores. Specifically, compared to their ruthenium(II)
analogues, osmium(II) complexes have larger d orbital splittings and lower oxidation
potentials (leading to higher-energy dd excited states and lower-energy MLCT excited
states), “larger” d orbitals (leading to metal-ligand n back-bonding enhancement), and
greater spin-orbit coupling.169
191

192
Although the 3-octylthiophene oligomers used in the synthesis are regioregular,
due to the constraints of the polymerization reaction the polymers are not regioregular.
Specifically, there exist three types of substituted bipyridines in the backbone: (1) 2,2’-
bipyridine substituted at the 5,5’-positions with two 3-octylthiophene units linked through
the 2-positions (the two “heads” of the oligomers); (2) 2,2’-bipyridine substituted at the
5,5’-positions with two 3-octylthiophene units linked through the 5-positions (two
oligomer “tails”); and (3) 2,2’-bipyridine substituted with the “head” of one and the “tail”
of another 3-octylthiophene oligomer. Despite the mixed structure of the polymer
backbones, there is no evidence that the heterogeneity has an influence on its
photophysical characteristics, and therefore we will not consider the point further.
The model complexes Ru(tpbpy)(bpy)22+ and Ru(tpbpy)32+ (where tpbpy = 5,5’-
bis(3-octylthiophene)-2,2’-bipyridine) were examined to provide insight concerning the
effect of thiophene substitution on the electrochemistry, photophysics and photoinduced
electron transfer reactivity of the Ru(II)-bipyridine chromophore. Note that Swager and
co-workers in a recent study60 reported details concerning the electrochemical and optical
absorption properties of the structurally related complexes, Ru(dtpbpy)(bpy)22+ and
Ru(dtpbpy)32+ (where dtpbpy = 5,5’-bis(5-(2,2’-bithienyl))-2,2’-bipyridine) and the
resulting polymers produced by oxidative electropolymerization. In general, the
electrochemical and UV-Visible absorption properties of these complexes are in direct
accord with these results.

193
Results
Photophysical parameters from various measurements for the thiophene model
complexes and polymers are listed in Tables 6-1 and 6-2, respectively. All photophysical
work was done in acetonitrile solutions under an inert atmosphere except for P4, where
THF solutions were used.
P4 : M = -
P4-Ru : M = [Ru(bpy)2][PF6]2
P4-Os : M = [Os(bpy)2][PF6]2
\ /
Ru(bpy)2¿
2PF6-
P6-Ru
Figure 6-1: Thiophene model complex and polymer structures.

194
Table 6-1: Thiophene model complex photophysics.
Ru(tpbpy)(bpy)22+
Ru(tpbpy)32+
Absorption
Aâ„¢x/nm
291 (7.74)
275 (4.89)
(Emax/ 104 M'1 cm’1)
331 (3.44)
337(6.71)
373 (4.08)
377(8.33)
459(1.41)
473(1.12)
Emission
A.298 k / nm
639
630
^em
0.16
0.18
*600 nm, 298 K / M'S
2.24
2.85
*600 nm, 80 K / PS
5.02
-
kr, 298 K / 104 S '
7.0
6.2
knr, 298 K / 105 S '
3.8
2.9
TA
*298 K / PS
1.19
3.21
Note: Measurements were conducted on argon bubble-degassed acetonitrile solutions prepared in a drybox.
Additional experimental conditions are discussed in the text.
Table 6-2: Thiophene polymer photophysics.
P4
P4-Ru
P4-Os
P6-Ru
Absorption
A-max / nm
(smax/104 M-1 cm1)
437(3.35)
476 (5.70)
290 (7.05)
All (4.80)
294 (6.39)
464 (6.95)
287(7.91)
Emission
A.298 k / nm
541
629
797
770
*298 K / PS
ti
o
i.
2.57
0.099
0.495
em
0.33
< 10’3
< 10‘3
< lo-4
TA
*298 K / PS
19.7
2.07
0.106
4.52
Note: Measurements were conducted on argon bubble-degassed acetonitrile solutions prepared in a drybox
for all polymers except TP1, where THF solutions were used. Additional experimental conditions are
discussed in the text.
Electrochemistry
Cyclic voltammetry was performed on CH3CN / 0.1 M TBAH solutions of the
model thiophene-bipyridine complexes and polymers, and relevant oxidation and

195
reduction half-wave potentials are listed in Table 6-3. For comparison, redox potentials
for Ru(bpy)32+ and Os(bpy)32+ in the same solvent medium are also included.
Comparision of the two tpbpy-substituted model complex redox potentials reveals
that their first oxidation and reduction potentials are shifted to more positive potentials
relative to Ru(bpy)32+ redox potentials. The shifts are consistent with the thiophene
substituents on the bpy ligands acting as u-electron acceptors. The positive shift is
greater for Ru(tpbpy)3 , indicating that the three tpbpy ligands have a combined effect on
both the metal center oxidation and tpbpy ligand reduction. Swager and coworkers60
observed similar anodic shifts for the first reduction potentials of the mono- and tris-
bithiophene complexes (Ru(dtpbpy)(bpy)2 and Ru(dtpbpy)3 ) but they did not report
the oxidations, apparently due to the propensity of their complexes to electropolymerize
at anodic potentials.
The model complex electrochemical data reveals that the first reduction of both
tpbpy complexes is localized on the tpbpy ligand, while the first oxidation wave
corresponds to the Ru(II/III) couple as shown in (6-1) and (6-2), respectively.
Ru“(tpbpy)(bpy)22+ +
e' -> RuII(tpbpy*')(bpy)2+
(6-1)
Ru"(tpbpy)(bpy)22+
e" -> Ru'"(tpbpy)(bpy)23+
(6-2)
The electrochemical properties of polymers P4, P4-Ru and P6-Ru were analyzed
in a previous report.170 However, features pertinent to the photophysical investigations
are summarized below. Comparision of the electrochemical data for the various polymers
allows assignment of the first two oxidation and first reduction waves observed for both
of the ruthenated polymers to redox processes centered on the thiophene-bipyridine

196
polymer backbone. For example, the first oxidation and reduction process for P4-Ru can
be represented as shown in (6-3) and (6-4), respectively.
Run(P4bpy)(bpy)22+ +
e' —» RuH(P4bpy*')(bpy)2+
(6-3)
Ru"(P4bpy)(bpy)22+
e' Run(P4bpy*+)(bpy)23+
(6-4)
In (6-3) and (6-4), P4bpy*' and P4bpy*+ represent a radical anion and polaron (radical
cation) localized on the ^-conjugated polymer backbone, respectively. In polymer
P6-Ru, the increased oligo(3-octylthiophene) segment length induces a cathodic (i.e., less
positive) shift in the first two oxidation and reduction waves. However, the assignment
remains the same. The Ru(II/III) wave occurs for P4-Ru at +1.40 V and for P6-Ru at
+1.34 V in CH3CN solution versus SCE.
For cathodic sweeps, the properties of P4-Os are similar to those of P4-Ru, where
the first reduction is centered on the P4bpy polymer backbone and the second is localized
on one of the “ancillary” osmium bipyridine ligands. However, anodic sweeps reveal an
important difference, where three closely-spaced oxidation waves were observed. Careful
comparison of the electrochemistry of the various polymers and model complexes as
shown in Figure 6-2 leads us to assign the first oxidation wave to the Os(II/III) couple as
shown in (6-5).
Osn(P4bpy)(bpy)22+ + e' -> Osni(P4bpy)(bpy)23+ (6-5)
The second and third oxidations are located on the thiophene segments of the P4bpy
backbone.

197
Table 6-3: Electrochemistry of thiophene complexes and polymers
Compound3
El/2, red
E1/2, oi
AE mb
Ru(bpy)32+
-1.26 (bpy0/*')
-1.45 (bpy0/-)
+1.30 (Ru1â„¢1)
2.57
Os(bpy)32+
-1.22 (bpy0/-)
-1.42 (bpy0/")
+0.88 (Os'â„¢1)
2.10
Ru(tpbpy )(bpy )22+
-0.99 (tpbpy0/-)c
-1.31 (bpy0/*T
+ 1.57 (Ru1â„¢1)0
2.56c
Ru(tpbpy)32+
-0.89 (tpbpy0/*')c
-1.18 (tpbpy0/*')c
+1.73 (Ru1â„¢1)0
2.62c
P4d
-1.78 (P4bpy0/-)
+0.97 (P4bpy0/*+)°
+1.35 (P4bpy*+/2+)e
2.75
P4-Ru
-0.99 (P4bpy0/-)
-1.27 [Ru(bpy)(bpy0/-)]
+0.97 (P4bpy0/,+)
+ 1.13 (P4bpy*+/2+)
+1.40 (Ru1â„¢1)
1.96
P6-Ru
-0.99 (P6bpy0/-)
-1.30 [Ru(bpy)(bpy0/*')]
+0.82 (P6bpy0/*+)
+0.98 (P6bpy*+/2+)
+1.34 (Rull/ni)
1.81
P4-Os
-0.91 (P4bpy0/-)
-1.14 [Os(bpy)(bpy0/-)]
+0.92 (Os1â„¢1)
+1.01 (P4bpy0/*+)
+1.21 (P4bpy*+/2+)
1.83
“Measurements performed in CH3CN solution (0.1 M TBAH supporting electrolyte) with a Pt working
electrode, Pt auxiliary electrode, and Ag/Ag+ (10'2 M) reference electrode. Potentials are referenced against
a ferrocene internal standard, and reported in V vs. SCE along with their assigned redox couple.
bDifference between lowest oxidizing and reducing waves. cCH2C12 / 0.2 M TBAH solution measurements.
dThin film immersed in CH3CN / 0.1 M TBAH solution. “Coulometry indicates that the first and second
oxidations correspond to 0.5 and 1.5 electrons, respectively. See reference 170 for details.
Absorption Spectra
Absorption spectra of the thiophene model complexes and polymers, with
absorptivity values calculated based on (3-1), are shown in Figure 6-3. Note that the
polymer absorptivity values are based on the formula weight of the repeat unit.
Absorption maxima are listed for the model complexes and polymers in Tables 6-1 and
6-2, respectively.

198
a)
J—►
E/V
Figure 6-2: Cyclic voltammetry in CH3CN solution / 0.1 M TBAH, with a Pt working
I 2
electrode, Pt auxiliary electrode, and Ag/Ag (10' M) reference electrode.
(a) [Os(bpy)3][PF6]2; (b) P4-Os; (c) P4-Ru; (d) [Ru(bpy)3]Cl2.

199
Figure 6-3: Thiophene model complex and polymer absorption spectra in acetronitrile
solutions (except P4, which is in THF).
The model complex absorption spectra feature two strong tpbpy-based intraligand
7T,7r* bands at 325 and 370 nm along with a weaker 450 nm MLCT band. The strong 370
nm intraligand band, which is considerably enhanced in the tris-tpbpy complex, is due to
the long axis-polarized n,n* optical transition on the tpbpy ligand. The large oscillator
strength in this transition is consistent with the extended 7r-conjugation produced by the
linear array of four heteroaromatic rings. The absorption maximum for the MLCT

200
9+
transition is red-shifted «14 nm for Ru(tpbpy)3 compared to that for the heteroleptic
complex Ru(tpbpy)(bpy)2 . However, the red side of the MLCT bands match well. In
the heteroleptic complex, the MLCT band contains contributions from Ru —> bpy and Ru
—> tpbpy transitions, while in the homoleptic complex the band arises from the Ru -»
tpbpy transition only. Since the electrochemical results indicate that the tpbpy ligand is «
200 mV easier to reduce than bpy, the Ru -> tpbpy MLCT transition occurs at a lower
energy than the Ru -> bpy MLCT transition. Consequently, the low energy side of the
MLCT band for both complexes is due to the Ru -> tpbpy transition. The intensity
increase on the higher energy side of the MLCT band for Ru(tpbpy)(bpy)22+ is due to the
higher energy Ru -> bpy transitions.
Another point of interest is the fact that the extended conjugation present in tpbpy
does not increase its MLCT transition oscillator strength. Mulliken theory163-16:1 indicates
that the intensity of a charge transfer transition is proportional to the transition dipole,
which increases with the excited state dipole moment. Therefore, the similar oscillator
strength for the MLCT transitions in the tpbpy complexes compared to Ru(bpy)32+ signals
that the MLCT excited state dipole moments are similar. Consequently, the extended
conjugation in the tpbpy ligand does not increase the excited state dipole moment. This
conclusion may not be a surprise, given that tpbpy has a “linear” geometry imposed by
the 5,5’-substitution pattern of the thiophene rings on the bpy unit. Indeed, an increase in
excited state dipole moment might be anticipated if the thiophene rings were present in
the 4,4’-positions as shown for the PPE-type oligomers in chapter 5. This idea is further
supported in the work by Swager and coworkers on bis(bithienyl)-substituted bipyridine
complexes.60 Specifically, when the bithienyl units are at the 4,4’-positions on the

201
bipyridine ligand, the MLCT band extinction coefficient is increased by > 50% relative to
Ru(bpy)32+.
The absorption spectra of the thiophene-bipyridine polymers all feature a single
broad absorption with a shoulder on the blue side of the band (Figure 6-lb). Polymer P4
exhibits a broad 437 nm absorption band that is due to the long-axis polarized 7i,7t*
transition.5 26,103,167 The molar absorptivity value, which is based on a repeat unit
consisting of four thiophene rings and one bipyridine, is very similar to that of a head-to-
tail 3-octyl(thiophene) hexamer (smax ~ 3.80 x 104 Nf’cm'1).37
Coordination of-Ru(bpy)22+ to the P4bpy bipyridine unit (polymer P4-Ru)
induces a red-shift and intensity increase in the predominant low-energy absorption band.
This change in the band energy and intensity arises for several reasons. First, while the
low-energy band is clearly dominated by the n,n* transitions localized on the polymer
backbone, the Ru -> bpy and Ru —> P4bpy MLCT transitions must augment the oscillator
strength of the band, possibly contributing as much as 25% of the total intensity. Second,
the 7r,7r* transition energy is decreased relative to the P4 value due to the fact that the
ruthenium coordination forces the bipyridine subunit into a planar conformation, which
increases the effective conjugation length of the polymer backbone and reduces the
LUMO energy. This trend is the same photophysical phenomena observed in the PPE-
type oligomer presented in previous chapters. Third, it is also possible that metal
coordination increases the electron-accepting capability of the bipyridine unit, which in
turn increases the thiophene —> bipyridine charge transfer contribution to the observed
7r,7r* optical transition. In addition to the prominent low-energy band, the P4-Ru
absorption features enhanced absorptivity in the 300 - 400 nm region and an additional

202
intense 290 nm band. This new band clearly arises from a n,n* transition localized on the
remote bipyridines, while the weaker broad features in the 300 - 400 nm region may arise
from metal-centered (dd) and/or higher-energy MLCT transitions localized on the -
Ru(bpy)22+ chromophore.40
The P6-Ru absorption spectrum exhibits many of the same features as the P4-Ru
spectrum, but the dominant low-energy band in P6-Ru displays an enhanced molar
absorptivity and increased bandwidth. The absorptivity increase arises from the increase
in the number of thiophene rings in the repeat unit. The increased bandwidth may also be
due to the longer thiophene segment, which may allow a greater number of backbone
conformations and an increased distribution of n,n* transition energies.
The P4-Os absorption spectrum is generally similar to P4-Ru with some subtle
yet significant differences. First, the red edge of the dominant low-energy absorption
band is shifted to slightly lower energy. This small shift may arise from allowed Os ->
bpy singlet-singlet MLCT transitions that are at a lower energy compared to the Ru -»
bpy transitions. This MLCT transition energy shift is anticipated since the osmium center
is considerably easier to oxidize than ruthenium (+0.89 vs. +1.37 V). By comparison, the
singlet-singlet MLCT transitions in acetonitrile solution of Os(bpy)32+ and Ru(bpy)32+
J A I 'll |
arise at 479 and 450 nm, respectively. ’ ’ Second, a weak band is clearly observed
for P4-Os in the 600 - 700 nm region, which is due to singlet-triplet Os -» bpy and Os -»
P4bpy MLCT transitions.
Emission Spectra and Decay Kinetics
Emission spectra of Ru(tpbpy)(bpy)22+ and Ru(tpbpy)32+ in optically dilute
acetonitrile solutions are shown in Figure 6-4, and the emission maxima are listed in

203
Table 6-1. The emission spectra were fitted by Franck-Condon emission bandshape
analysis based on (2-14) as shown in the figure, and fit parameters are listed in Table 6-4.
500 600 700 800
Wavelength / nm
Figure 6-4: Thiophene model complex emission spectra in acetonitrile (380 nm
excitation). Points are experimentally-determined data, while the lines are Franck-
Condon bandshape analysis fits as described in the text, (a) Ru(tpbpy)(bpy)22+; (b)
Ru(tpbpy)32+.
Table 6-4: Franck-Condon emission bandshape fitting parameters for model complexes.
Parameter
Ru(tpbpy)(bpy)22+
Ru(tpbpy)3i+
Eo / cm'1
15,795
15,925
hom / cm'1
1,300
1,350
Sm
0.91
0.86
Auo,i/2 / cm'1
1,420
1,370
Note: Emission fitting based on (2-14) and room temperature emission spectra recorded in dilute
acetonitrile solutions.

204
Both complexes feature broad emission bands with well-defined (0,0) and (0,1)
vibronic components. The spacing of the individual vibronic components (Avo,i/2 * 1400
cm'1) is consistent with C-C stretching modes centered on the bpy and tpbpy ligands. The
emission bands for the two complexes are slightly red-shifted relative to the emission of
Ru(bpy)32+ (Xmax = 615 nm).173 However, the overall similarity of the emission
bandshape and energies for the thiophene-subsituted complexes and the parent complex
strongly suggests that the emission emanates from a MLCT-based excited state for the
model complexes. The decreased emission energy for the tpbpy complexes is consistent
with the decreased tpbpy reduction potential compared to bpy and signals that for both
Ru(tpbpy)(bpy)22+ and Ru(tpbpy)32+ the lowest lying MLCT excited state is based on the
Ru —> tpbpy transition as shown in (6-6) for Ru(tpbpy)(bpy)22+.
Ru”(tpbpy)(bpy)22+ + hv -> RuIII(tpbpy*')(bpy)22+* (6-6)
The emission energy is slightly higher for Ru(tpbpy)32+ than for
Ru(tpbpy)(bpy)22+, consistent with the electrochemistry results. The MLCT state energy
(Emlct) is proportional to the difference in the metal center oxidation potential and the
acceptor ligand reduction potential (AEi/2 = Ei/2(Ruii/hi) - Ei/2(tpbpy0/*')), and
examination of the entries in Table 6-3 indicates that AEi/2 is larger for Ru(tpbpy)32+ than
Ru(tpbpy)(bpy)22+.
The photoluminescence spectrum of Ru(tpbpy)(bpy)22+ was also examined in a
4:1 EtOH/MeOH solvent mixture over a 80 K - 298 K temperature range (data not
shown). As temperature decreases, the emission intensity increases, the emission
maximum blue-shifts (Xmax = 595 nm at 80 K), and the vibronic progression becomes
better defined. The 0.14 eV anti-Stokes shift that occurs upon cooling is consistent with a

205
“rigidochromic” effect observed in MLCT emission of other d6 polypyridine metal
complexes* and further supports the assignment of the luminescence to the Ru —> tpbpy
MLCT excited state.41
Emission quantum yields and decay lifetimes were measured for
Ru(tpbpy)(bpy)22+ and Ru(tpbpy)32+ at 298 K, and the values are listed in Table 6-1.
Radiative and apparent non-radiative decay rates (kr and knr) were computed for both
complexes using the the above table. The apparent knr value represents the sum of the rates of the intrinsic
non-radiative decay process and internal conversion to a dd excited state that is
energetically accessible via thermal activation at 298 K. In addition, there may be further
complications in the excited state decay kinetics arising from the close energetic
proximity of a tpbpy ligand-centered 7i,7i* state.
The quantum yields and lifetimes for both tpbpy complexes are larger than those
for Ru(bpy)32+ (em = 0.062 and Tem = 840 ns in acetonitrile).40,76 The enhanced values for
the model thiophene-bipyridine complexes arise mainly due to a decrease in the apparent
non-radiative decay rate. The reduced apparent knr values for the tpbpy complexes likely
originate from a combination of two effects. First, the MLCT energy decrease in the
tpbpy complexes increases the energy gap between the MLCT and dd states, thereby
decreasing the rate of internal conversion. Second, the extended 7r-conjugation in the
tpbpy ligand increases the delocalization of the photoexcited electron which is likely to
reduce the excited state electron-vibration coupling. In recent studies174,175 it has been
demonstrated that delocalization in the acceptor ligand effectively decreases knr.
* Ru(bpy)32+ features a 0.17 eV blue-shift on cooling.40

206
Emission and excitation spectra of the thiophene-bipyridine polymers in optically
dilute room temperature solutions are illustrated in Figure 6-5 and emission maxima,
quantum yields and decay lifetimes are listed in Table 6-2. The emission spectrum of P4
in THF features a relatively intense 541 nm band and a 569 nm shoulder, with a quantum
yield of 0.32. Unfortunately, the emission decay lifetime is too short to measure
accurately with our instrumentation, so we conclude that x < 200 ps. The small Stokes
shift, large quantum yield and short lifetime all suggest that photoluminescence from P4
emanates from a ’71,71* exciton that is energetically located near the material band edge.
The overall fluorescence properties of P4 do not differ substantially from that of a
regioregular head-to-tail poly(octylthiophene),36 indicating that the bipyridine unit has a
relatively minor effect on its lowest excited state properties. Although phosphorescence
was not observed from P4, in view of the similarity of the ’7:,71* photophysics of this
polymer to that of head-to-tail poly(octylthiophene), the P4 371,71* state can be estimated at
approximately 1.6 ± 0.1 eV. This estimate is based on a recent study of thiophene
oligomers that suggests the singlet-triplet splitting in polythiophenes is « 5200 cm'1.30
The P4-Ru photoluminescence (Figure 6-5b) has a similar energy and bandshape
compared to Ru(tpbpy)(bpy)22+ and Ru(tpbpy)32+ (Figure 6-4). This feature strongly
implies that the P4-Ru photoluminescence emanates from the Ru —> P4bpy MLCT
excited state. However, the P4-Ru emission quantum yield is at least two orders of
magnitude lower than the model complexes (Tables 6-1 and 6-2). In spite of the
dramatically reduced quantum yield, the P4-Ru emission lifetime (2.57 ps) is comparable
to that of the model complexes. This combination of very low quantum yield and large

207
lifetime suggests an apparent radiative decay rate for P4-Ru that is unusually low
compared to other polypyridine Ru(II) complexes (kr» 103 s'1 vs. 10‘ s’1). This situation
has been observed by Schmehl and coworkers112147 in styryl-bipyridine and pyrene-
bipyridine Ru(II) complexes where there is an intraligand 3n,n* excited state that lies
close in energy to the emitting MLCT excited state. By inference, we believe that the
unsually weak P4-Ru MLCT luminescence arises because the energy of the P4bpy
“ligand” 37i,7t* state (EtP4) is 0.3 - 0.4 eV less than the MLCT energy (Emlct) and
consequently is the dominant excited state species present at long times after
photoexcitation. ' If this scenario is correct, the MLCT emission arises via thermally-
activated internal conversion from the P4bpy 37i,7T* state. This situation is analogous to
the observation of delayed fluorescence in organic chromophores.108
Polymer P6-Ru features an exceedingly weak 760 nm emission (Figure 6-5c).
This emission is red-shifted and considerably weaker (* 20-fold weaker, the P4-Ru emission. Unfortunately, the emission is too weak to obtain reliable decay
lifetime data. Given the energy and bandshape of this emission, it is safe to conclude that
P6-Ru does not luminesce from a Ru -> P6bpy based MLCT state. MLCT emission is
absent in P6-Ru because the P6 37i,7i* state energy (ETP6) is even lower than the P4 triplet
energy (i.e., EjP6 < EtP4). This idea is supported by a recent study which demonstrated
that the triplet energy in a-oligothiophenes decreases by approximately 0.06 eV per
thiophene unit (for n = 3 to 7).30 Based on this study, we anticipate EjP6 may be at least
0.1 eV less than EjP4. The decreased P6-Ru triplet energy may preclude significant
population of the ruthenium-based MLCT state via thermally activated internal

208
conversion, and consequently MLCT emission is not observed. Finally, it is tempting to
consider the fact that the weak emission observed from P6-Ru may emanate directly from
â– j
the 7i,7i* manifold (i.e., the emission is phosphorescence). Based on the emission energy,
this would place EjP6 « 1.5 - 1.6 eV. This phosphorescence conclusion is based on its
similarity to an 826 nm phosphorescence band observed for poly(3-hexylthiophene) at 18
K.38
Polymer P4-Os features a relatively weak 797 nm emission (Figure 6-5d). This
emission is red-shifted « 0.45 eV compared to the P4-Ru MLCT emission. However,
based on the difference in the emission energies of the parent complexes (Ru(bpy)32* and
Os(bpy)32+, 0.35 eV),171 the P4-Os emission energy is in accord with expected results if
the luminescence emanates from the Os -» P4bpy MLCT state. The MLCT assignment is
also supported by the lifetime (xem = 100 ns), which is consistent with MLCT state
lifetimes in osmium polypyridyl complexes that have emission energies similar to that of
P4-Os.76 Since the luminescence properties are similar to those observed for osmium
polypyridine complexes, we conclude that in P4-Os the MLCT state is not significantly
“perturbed” by the P4 37t,7t* state. Therefore, in P4-Os Emlct < ETP4. In summary, the
P4-Ru and P4-Os observations imply that ETP4 is less than Emlct for the -Ru(bpy)22+
chromophore but greater than Emlct for the -Os(bpy)22+ chromophore (i.e., 2.0 eV > EtP4
> 1.55 eV). Note that this implication agrees with the estimated P4bpy “ligand” triplet
energy given above (« 1.6 ± 0.1 eV).

209
Wavelength / nm
Figure 6-5: Thiophene polymer emission (solid line) and excitation (dashed line) spectra
in optically dilute acetonitrile solution (except P4, which is in THF solution).
(a) P4 (400 nm excitation; 540 nm emission); (b) P4-Ru (380 nm excitation; 630 nm
emission); (c) P6-Ru (460 nm excitation; 760 nm emission); (d) P4-Os (475 nm
excitation; 800 nm emission).

210
An important feature that is shared by all metal-organic polythiophenes is the
absence of any significant '71,71* fluorescence from the polymer backbone. Fluorescence
emission is not observed despite the fact that 1) the absorption spectra of the polymers are
dominated by the '71,71* bands and 2) the radiative decay rate of the '71,71* state is large.
These observations suggest that the '71,71* exciton produced by light absorption in the
metal-organic polymers diffuses to and becomes trapped by the metal complex units very
rapidly with a rate in excess of IO" s'1. This conclusion is in accord with recent studies
of intra- and inter-strand energy migration in conjugated polymers discussed in chapter 1
which suggest that '71,71* excitons are highly mobile in 71-conjugated assemblies.
Transient Absorption Spectra
Transient absorption spectra were recorded for the thiophene-bipyridine model
complexes and polymers following 355 nm excitation. Transient absorption decay
lifetimes obtained from global factor analysis'14 of the time-resolved absorption data are
listed in Table 6-1 for the model complexes and Table 6-2 for the polymers.
The transient absorption difference spectra for Ru(tpbpy)(bpy)22+ and
Ru(tpbpy)32+ are illustrated in Figures 6-6a and 6-7a, respectively. Transient absorption
decay lifetimes for both complexes are in approximate agreement with the MLCT
luminescence decay lifetimes, suggesting that the transient absorptions arise from the
MLCT excited state. The similarity of the transient absorption difference spectra for the
two complexes suggests similar MLCT excited state electronic structures. By contrast,
the excited state difference spectra of the tpbpy complexes are very different from the
difference spectrum of Ru(bpy)32+, where a 360 nm absorption and 440 nm MLCT bleach

211
• 1 7
is observed. Therefore, we conclude that the long-lived MLCT state in the tpbpy
complexes is based on the Ru -> tpbpy transition shown in (6-6) above.
Figure 6-6: Transient absorption spectra of Ru(tpbpy)(bpy)22+ in acetonitrile. Arrows
indicate progression of the transients with time after 355 nm laser excitation, (a) complex
only (transients are 800 ns increments after laser excitation); (b) complex with 20 mM
MV2+ (transients are 80 ns increments after laser excitation).

212
Figure 6-7: Transient absorption spectra of Ru(tpbpy)32+ in acetonitrile. Arrows indicate
progression of the transients with time after 355 nm laser excitation, (a) complex only
(transients are 1600 ns increments after laser excitation); (b) complex with 20 mM MV2+
(transients are 4000 ns increments after laser excitation).
Several points are of interest with respect to the transient absorption spectra of the
model complexes. First, given that tpbpy is the MLCT state “acceptor ligand”, the
excited-state transient absorption spectrum is dominated by features associated with the
one-electron reduced state of the ligand (i.e., tpbpy*'). This conclusion is clearly the case
since the most pronounced feature in the difference spectrum is the 380 nm bleach that

213
corresponds to the ground-state n,n* absorption of the tpbpy ligand. In addition, two
strong excited-state absorption bands are observed in the visible region which likely arise
from allowed 7t -» n* and n* -> n* transitions localized on tpbpy*'. Furthermore, the
lack of an observable bleach of the ground state MLCT absorption band in the 400 - 450
nm region (s * 15,000 M 'cm'1) seen in the Ru(bpy)32+ difference spectrum qualitatively
indicates that the oscillator strength of the excited state absorption bands seen in the
visible region are large (e > 20,000 Nf'cm'1). These large oscillator strengths also
correspond to the visible transient absorption bands arising from transitions associated
with tpbpy*'.
The transient absorption difference spectrum of P4 in THF is shown in Figure 6-7.
The spectrum features bleaching at 440 nm that corresponds to the ground-state n,n*
absorption and a broad excited-state 740 nm absorption band that extends into the near-
IR. The transient absorption decays with t » 20 ps,t which is a strong indication that the
transient is the 37r,7i* state. In accord with the triplet assignment, the transient absorption
difference spectrum of P4 is remarkably similar to the triplet-triplet difference spectra of
poly(3-octylthiophene) (7.max = 820 nm)132, a-septithiophene (Figure 1-8, A.max = 740
nm)28,29 and the PPE-type oligomers previously discussed (Figure 3-9). The transient
absorption of P4 is comparatively weak (AAmax » 0.02), which is a qualitative indication
that the triplet yield following direct excitation of the polymer is low (likely < 20%).
t The P4 transient lifetime is likely limited by the presence of residual oxygen after argon
bubble-degassing.

214
Figure 6-8: Transient absorption spectra of P4 in argon bubble-degassed THF. Arrows
indicate progression of the transients with time after laser excitation, and transients are
1600 ns increments after laser excitation.
Transient absorption difference spectra for P4-Ru and P6-Ru are illustrated in
Figures 6-9a and 6-10a, respectively. The difference spectra of the ruthenated polymers
are qualitatively similar to the P4 difference spectrum, which suggests that the P4-Ru and
P6-Ru transient absorption arises from the thiophene-bipyridine polymer backbone 37i,7i*
excited state. However, despite the triplet assignment, the transient absorption decay
lifetimes of P4-Ru and P6-Ru are considerably shorter than the P4 triplet state.
Furthermore, there is good agreement in P4-Ru between the transient absorption and
photoluminescence decay lifetimes. This correlation is surprising given that the
photoluminescence of P4-Ru has been assigned to the Ru ->â–  P4bpy MLCT state. These
features suggest that the 37t,7i* decay dynamics may be modified in P4-Ru and P6-Ru due

215
to its close energetic proximity to the MLCT state. This point will be discussed in more
detail below.
400 500 600 700 800
Wavelength / nm
Figure 6-9: Transient absorption spectra of P4-Ru in acetonitrile. Arrows indicate
progression of the transients with time after 355 nm laser excitation, (a) polymer only
(transients are 800 ns increments after laser excitation); (b) polymer with 20 mM MV2+
(transients are 4000 ns increments after laser excitation).

216
Figure 6-10: Transient absorption spectra of P6-Ru in acetonitrile. Arrows indicate
progression of the transients with time after 355 nm laser excitation, (a) polymer only
(transients are 1600 ns increments after laser excitation); (b) polymer with 20 mM MV
(transients are 8000 ns increments after laser excitation).
The P4-Os transient absorption difference spectrum is shown in Figure 6-1 la.
The spectrum exhibits a 490 nm ground-state bleach similar to that observed in P4-Ru
and P6-Ru. However, the excited-state absorption of P4-Os in the 600 - 800 nm region
is much less prominent than the corresponding ruthenated polymer (i.e., the absorption of
P4-Os is relatively “flat” without any discernible maximum in the 600 - 800 nm region).

217
Furthermore, the P4-Os transient absorption decay lifetime is in excellent agreement with
the emission decay lifetime (Table 6-2). These features point to the possibility that for
P4-Os the transient absorption arises from the Os —» P4bpy MLCT state and not the
polymer backbone state.
d)
o
c
re
A
L_
o
to
A
<
<
400 500 600 700 800
Wavelength / nm
Figure 6-11: Transient absorption spectra of P4-Os in acetonitrile. Arrows indicate
progression of the transients with time after laser excitation, (a) polymer only (transients
are 24 ns increments after laser excitation); (b) polymer with 20 mM MV2+ (transients are
48 ns increments after laser excitation).

218
Discussion
Excited-State Energetics
Based on the luminescence and transient absorption spectroscopy of the various
thiophene-bipyridine polymers, it is possible to assemble a relatively concise scheme that
explains the experimental observations. This scheme is summarized in the Jablonski
diagrams shown in Figure 6-12, where the energies of the various states are defined as
accurately as possible.
3.0
2.5
LU
0
Figure 6-12: Thiophene-bipyridine polymer Jablonski diagram.
First, consider the situation for the two ruthenated polymers, P4-Ru and P6-Ru,
which are shown on the left side of the figure. Photoexcitation in the near-UV and visible
region primarily populates the '71,71* state of the Pnbpy polymer (path 1). This state
rapidly decays to the 3n,n* state of the Pnbpy backbone, which is the lowest excited state

219
in the “supermolecule”. It is unknown whether this process occurs via heavy atom
promoted direct intersystem crossing (path 3) or the 3MLCT state (path 2 followed by
path 4). However, it is certain that the process occurs rapidly and efficiently, given the
complete absence of '71,71* fluorescence and the comparatively high yield of the long-
lived excited state based on the strength of the transient absorption signal. For both
P4-Ru and P6-Ru, the long-lived excited state observed by ns-ps transient absorption
2
spectroscopy is the 7i,7i* state. Although the population of the excited state polymer
â– 2 2
molecules predominantly exists in the n,n* state, the MLCT state can be repopulated
via a thermally-activated internal conversion process (step 5). In this way, an equilibrium
is established between the two states.147,148 In P4-Ru, the energy gap between the 37i,7i*
and 3MLCT states is small enough so that at equilibrium there is a sufficient population
of 3MLCT to observe its characteristic emission (path 6). However, in P6-R11 the energy
gap separating these states is apparently large enough to suppress the MLCT emission.
Nonetheless, in both P4-Ru and P6-Ru the dominant pathway for 3 71,71* state decay is via
the 3MLCT state (i.e., path 5 followed by path 7). Note that the increased 3 71,71* state
lifetime in P6-R11 relative to P4-Ru is consistent with the larger energetic deficit that
needs to be overcome to return to the MLCT state. This excited-state equilibrium is
identical to that observed in the PPE-type oligomers presented in previous chapters.
The P4-Os excited state scheme is outlined in the Jablonski diagram on the right
side of Figure 6-12. Near-UV and visible excitation of this polymer (path 1) affords the
P4bpy backbone '71,71* state. This state rapidly relaxes to the Os —> P4bpy 3MLCT state
(path 2), which is the lowest excited state of the “supermolecule”. The 3MLCT state then
relaxes by normal radiative and non-radiative decay pathways (paths 3 and 4), giving rise

220
• • • O-}-
to the luminescence spectrum and lifetime that are typical for the Os(bpy)3
chromophore.
Electron Transfer Energetics
In an effort to investigate the propensity of the excited state polymers to undergo
photoinduced electron transfer (ET) and to characterize the spectroscopic properties of
the oxidized and/or reduced forms of the polymers, transient absorption studies were
carried out on the model complexes and P4-Ru, P6-Ru and P4-Os in the presence of
N,N’-dimethylaniline (DMA, a reductive quencher) and N,N’-dimethyl-4,4’-bipyridinium
(MV , an oxidative quencher).
Addition of 20 mM DMA did not result in excited state quenching (as assessed by
transient absorption) for any of the complexes or polymers. The lack of quenching is
consistent with free energy estimates for ET (calculated below) that indicate reductive
quenching by DMA is endothermic by at least 0.1 eV for all of the materials. By contrast,
MV quenches the transient absorption of all of the ruthenium complexes and metallated
polymers. Furthermore, in almost every case quenching leads to the production of long-
lived transient absorptions that clearly arise from the products of bimolecular
photoinduced ET. The ET rate constant (k^t) for these model complexes and polymers are
calculated based on (6-7).
In (6-7), k[j is the M* decay rate constant without the presence of the methyl viologen
quencher and ket is the decay rate constant at a specific viologen concentration.
Calculated electron transfer rate constants are listed in Table 6-5.

221
Table 6-5: Electron transfer rate constants for thiophene-bipyridine models and
polymers.
Compound8
C /105 s'1 b
kobs /106 s'1'
[MV2+1 / mM
K, / 107 M 1 s’1
Ru(tpbpy )(bpy )22+
8.40
5.90
20
25.3
Ru(tpbpy)32+
3.12
1.19
22
3.99
P4-Ru
4.83
5.25
30
15.9
P6-Ru
2.21
1.60
21
6.57
P4-Os
a a .. _ 1 J
100
15.3
20
26.5
quencher. Transient absorption decay rate in the presence of the specified methyl viologen concentration.
Figures 6-6b and 6-7b illustrate the evolution of the transient absorption spectra
when a solution of Ru(tpbpy)(bpy)22+ or Ru(tpbpy)32+ and 20 mM MV2+ is subjected to
355 nm excitation. At early times after excitation, the MLCT excited state absorption is
apparent. However, over the course of « 1 ps the spectrum evolves into one that is
characterized by bleaching for A < 380 nm, a strong 395 nm absorption with a 400 nm
shoulder, weak bleaching between 440 and 480 nm and a broad 605 nm band. This
difference spectrum is clearly due to a superposition of absorption bands characteristic of
the oxidized Ru(III) complex and the viologen radical cation, MV+\153 These species are
produced by the photoinduced ET described in (6-8).
Ru,II(tpbpy")(bpy)22+* + MV2+ -> Ruin(tpbpy)(bpy)23+ + MV+* (6-8)
The transient absorption decays on a longer timescale (t « 50 ps) consistent with the
disappearance of radical ions via diffusion-controlled back ET. The excited state
quenching rate for Ru(tpbpy)32+ is approximately six times lower than Ru(tpbpy)(bpy)22+
(Table 6-5).

222
There are several significant features with respect to the ET quenching
experiments on the model complexes. First, although both complexes are quenched by
MV2+, the quenching rates are an order of magnitude less than the rate that MV2+
quenches Ru(bpy)32+ (ket = 2.4 x 109 M'V1).177 The reduced quenching rates are easily
explained by the fact that the excited state oxidation potentials for the tpbpy complexes
are considerably less negative than Ru(bpy)32+ (Ei/2(M2+*/M3+) «-0.81 V vs SCE).178
The excited state tpbpy complexes are less powerful reducing agents because the 71-
acceptor nature of the tpbpy ligand 1) renders the ground complexes harder to oxidize and
2) lowers Emlct- Next, it is clear that the difference absorption spectrum corresponding
to the ET products in (6-8) is dominated by the MV+* absorption, indicating that the
absorption difference between Ru"(tpbpy)(bpy)22+ and Runi(tpbpy)(bpy)23+ is relatively
small. However, there is one feature worth noting: the X < 380 nm bleach coupled with
the 410 nm shoulder implies that the tpbpy ligand long-axis polarized n,n* absorption is
slightly red-shifted in RuHI(tpbpy)(bpy)23+. This red-shift likely occurs because the more
electrophilic Ru(III) metal center increases the 7t-acceptor nature of the bipyridine unit,
thereby slightly increasing the thiophene —» bipyridine CT contribution to the 7i,7r*
transition.
The transient absorption difference spectra of P4-Ru and P6-Ru in the presence
•y,
of 20 mM MV are illustrated in Figures 6-9b and 6-10b, respectively. Methyl viologen
efficiently quenches the excited state absorption of both complexes (Table 6-5), and the
quenching is accompanied by very significant changes in the transient absorption spectra.
Specifically, for P4-Ru the quenching products feature the 395 nm MV+# absorption
along with a very strong 735 nm absorption band and a 600 nm shoulder. For P6-Ru, the

223
395 nm band due to MV+* is also observed, but the strong absorption band in the red is
shifted to 800 nm (or above). The very strong absorption bands in the red that are
produced by oxidative quenching of P4-Ru and P6-Ru correspond remarkably well with
the absorption bands of the cation radicals of quaterthiophene (Xmax = 650 nm, shoulder to
the blue) and sexithiophene (X,max = 780 nm, shoulder at 690 nm).179,180 Therefore, it is
clear that oxidative quenching of the two ruthenated polymers affords the corresponding
oxidized polymers where the charge resides on the thiophene oligomer segments (i.e.,
Ru1I(P4bpy+*)(bpy)23+ and Run(P6bpy+’)(bpy)23+). By comparing the intensity of the
MV+* band at 395 nm(s = 30,000 Nf’cm'1) and the red bands due to P4bpy+* and
P6bpy+*, the molar absorptivity of the thiophene-based polarons can be estimated, e «
70,000 IVT'cnT1.
Figure 6-1 lb shows the transient absorption spectrum of P4-Os in the presence of
20 mM MV . In this case, MV clearly quenches the excited state (« 50% quenching is
achieved at [MV2+] = 20 mM). However, only weak absorption due to MV+* at 395 nm is
observed, along with ground-state bleaching between 400 - 500 nm and weak absorption
above 500 nm. Although it is clear that photoinduced ET occurs when P4-Os is
quenched by MV2+, the lack of a strong absorption band due to the P4bpy+* polaron state
is significant. Consideration of the electrochemical data provides an explanation for this
apparent anomaly. In P4-Os, the first oxidation occurs at the metal center, and
consequently the one-electron oxidized state of the material has the hole on the metal
center rather than on the P4bpy backbone (i.e., OsHI(P4bpy)(bpy)23+). Because of this
situation, the difference absorption spectrum of the oxidized polymer is not very

224
pronounced because the Os(III) ion induces only a small perturbation in the polymer
backbone electronic structure.
The final point that must be considered concerns the correlation between the
observed ET quenching rates and the ET driving force. Table 6-6 summarizes the excited
state oxidation potentials and free energy for photoinduced ET to MV2+ and DMA (AGE r)
as calculated in (6-9).
AOET=E„-Eral (6-9)
In order to obtain the proper redox potentials for the metal complex excited state, the
excited state energy must be included with the redox measurements as described in
(6-10).
e(m*/M")=e(m/M“)+E00 (6-10a)
e(m+/M*)=e(m+/m)-E00 (6-10b)
In (6-10), Eoo is the zero-zero excitation energy of the excited-state transition (i.e., the
MLCT transition). If we consider the electrochemistry and spectroscopy data above
along with the dimethylaniline oxidation half-wave potential (+ 0.88 V vs. SCE)181 and
methyl viologen reduction half-wave potential (- 0.46 V vs. SCE) in acetonitrile,97 the
free energy changes can be calculated.

Table 6-6: Electron transfer free energy changes for thiophene-bipyridine models and polymers.
Molecule”
E(M / M)
E(M+ / M)
E(P / P+)
Eoo
E(M*/M‘)
E(M+ / M*)
E(P+/P*)
AGet (DMA)
AGet (MVJ+)b
AGet (MV!t)c
Ru(tpbpy)(bpy)22+
-1.16
+ 1.36
-
1.96
+0.80
-0.60
-
+0.08
-0.14
-
Ru(tpbpy)32+
d
+ 1.40
-
1.97
d
-0.57
-
d
-0.11
-
P4-Ru
-0.99
+ 1.40
+0.97
1.97
+0.98
-0.57
-1.00
-0.1 of
-0.11
-0.54
P6-Ru
-0.99
+1.34
+0.82
(1.97)'
+0.98
-0.63
-1.15
-0.1 of
-0.17
-0.69
P4-Os
-0.91
+0.92
-
1.56
+0.65
-0.64
-
+0.23
-0.18
-
aAll values are in volts versus SCE except for AG°, which is in eV. All measurements were made in acetonitrile solutions. Eoo values are taken from Franck-
Condon emission bandshape fitting or the emission band maximum. bThermodynamic driving force based on metal oxidation potential. ‘Thermodynamic driving
force based on Pnbpy oxidation potential. dNo reduction observed due to absorption on the working electrode. 'Since no MLCT emission was observed for P6-
Ru, the P4-Ru value is used in the calculation. The slight exothermic value may be due to errors in determining E00.

226
In each case, the excited state oxidation potentials for the complexes and polymers
are computed using the first oxidation potential and the observed emission energies. In
addition, a second set of entries is listed for P4-Ru and P6-Ru. These entries are
computed using the Rull/In potentials rather than the first oxidation potential that is based
on P4bpy backbone oxidation. In effect, P4-Ru and P6-Ru have significantly higher
reducing power in the excited state than the model complexes if the polymer-based
oxidation is used in the free energy calculation. The implication of this result is clear:
photoinduced ET with P4-Ru and P6-Ru must occur in a step-wise fashion involving the
sequence illustrated in Figure 6-13. Thus, we suggest that the reactive excited state for
ET from these polymers to MV is the Ru -» P4bpy MLCT state (this state is present in
an equilibrium with the Pnbpy-based 37t,7i* state). Photoinduced ET (step 1) affords the
oxidized polymer in a state where the hole is centered on the metal. In a second (thermal)
intramolecular ET reaction (step 2), the hole is transferred from the metal center to the
P4bpy backbone affording the long-lived polaron state. Note that the driving force for the
overall ET reaction written in (6-8) is given by the sum of the free energies for the two
individual steps (AGet' + AGet2); however, the driving force for photoinduced ET
calculated with the Ru1,/ni oxidation is given by AGet' only. This discrepancy accounts
for the higher than expected photoinduced ET rate when AG is computed using the first
(polymer-based) oxidation potentials.
A final point of interest concerns the application of Figure 6-13 to photooxidation
of P4-Os by MV2+. In this case, since the stable redox isomer of the oxidized polymer
has the hole on the Os center, photoinduced ET (step 1) directly affords the stable redox

227
isomer of the oxidized polymer. This species persists until back ET occurs (step 4) to re¬
generate the ground state polymer.
M"(3P4bpy*)(bpy)2
AGet1
AGet2
E
Figure 6-13: Photoinduced electron transfer process from M(P4bpy)(bpy)22+ to MV2+.
Implications of this Work
A detailed electrochemical and photophysical investigation has been carried out
on a novel series of metal-organic polymers that contain d6 transition metal polypyridine
complexes interspersed within a poly(3-octylthiophene) ^-conjugated network. The
properties of these metal-organic materials clearly indicate that the metal centers interact
strongly with the ^-conjugated system. This interaction gives rise to properties that are
not simply predictable based on the sum of the component molecular electronic systems.
A central objective of this study was to prepare soluble rr-conjugated materials
that display strong, long-lived MLCT photoluminescence characteristic of Ru(II)- and
Os(II)-bipyridine complexes. Although in most cases these polymers feature MLCT
luminescence, the efficiency is relatively low due to the “intrusion” of the energetically

228
i
low-lying 7i,ti* state of the 7i-conjugated thiophene-bipyridine system. Although the
objective of producing materials that are strongly photoluminescent was not achieved, the
work provides good insight into the steps that need to be taken in order to produce
strongly photoluminescent metal-organic materials. Specifically, it is clear that to
produce metal-organic materials that display efficient MLCT emission it is necessary to
keep the 37i,7i* states of the 7i-conjugated system above the energy of the MLCT states.
The PPE-based oligomers in previous chapters exhibit this same energetic trend. Given
the singlet-triplet splitting that is typical of PPV, PPE and polythiophenes (i.e., 0.6 - 0.7
eV),30,65 and the energies typical of strongly photoluminescent MLCT states (2.0 eV or
above), the 7i-conjugated system bandgap must be > 2.6 eV (475 nm) to have efficient
MLCT emission. This concept has been demonstrated in recent work from our
laboratories in which efficient MLCT photoluminescence has been observed from PPE-
type oligomers and polymers that contain the -Ru(bpy)22+ chromophore which fluoresce
at 440 nm.124
Finally, another important finding in this study is that despite the fact that the
MLCT states are not strongly luminescent, the metal-organic materials feature the
photoredox activity characteristic of MLCT chromophores. This finding is significant,
because strong photoredox activity is necessary to produce materials that perform well in
photoconductivity applications.

229
Experimental
Model Complex and Polymer Synthesis
The thiophene model complexes and polymers were synthesized by Lise Trouillet
and Stephan Guillerez at CEA-Grenoble, and all synthesis has been published.167,170,182
Methyl viologen synthesis. 1.6 g (0.01 mol) of 4,4’-dipyridine and 3.6 g (0.025
mol) of methyl iodide were added to a pyrex tube, which was sealed after freeze-pump-
thaw degassing. The sealed tube was heated in a 90 °C sand bath for two days. The
resulting brownish solid was dissolved in 100 ml of deionized water. A 50 ml water
solution containing 4.5 g (0.027 mol) of ammonium hexafluorophosphate was added to
the reaction mixture, immediately producing a yellow precipitate. The precipitate was
collected by filtration on a medium-porosity glass frit and air dried. The product
precipitate was purified by recrystallization from hot ethanol, isolating 4.5 g of pure
product.
Photophysical Measurements
All sample solutions studied were in distilled acetonitrile unless otherwise noted.
Note that all samples and solutions were handled under an inert atmosphere shielded from
light to avoid sample decomposition. Additional argon sample degassing was performed
after the initial sample preparation to ensure consistent sample degassing. All
photophysical studies were conducted with the same instrumentation and techniques
described in chapter 3.

230
Electrochemical Measurements
Electrochemical measurements were performed using PAR 173, 175, and 179
units from EG&G Princeton Applied Research connected to a SEFRAM TGM 164 or a
KIPP&ZONNEN BD 91 recorder. Methylene chloride and acetonitrile solutions were
used with 0.2 and 0.1 M TBAH, respectively, as a supporting electrolyte. A three-
electrode cell was used with a Ag / Ag+ (AgNC>3, 10'2 M) nonaqueous reference electrode,
platinum disk working electrode (0.07 cm2) and platinum wire auxiliary electrode.
Reference electrodes were calibrated with a ferrocene (Fc) internal standard, and all
potentials are listed versus SCE (+0.425 V vs. Fc / Fc+).

CONCLUSIONS
In the previous chapters, the extensive photophysics of three series of PPE-type
oligomers and one series of polythiophenes, each containing a central 2,2’-bipyridine unit
to allow MLCT chromophore incorporation into the 71-backbone, have been presented.
Several trends and conclusions can be made when examining these data:
1. Metal chromophore coordination to the oligomer or polymer increases the n-
conjugation. As discussed in chapter 1, the twisted bipyridine serves as a break in the
oligomer/polymer backbone rc-conjugation. When the MLCT chromophore is ligated to
this bipyridine, the geometry is forced to a planar configuration. This geometric change
increases the backbone conjugation and alters the observed photophysics, as seen in the
oligomer/polymer ground-state absorption bands that red-shift upon coordination. This
shift is due to a lowering of the LUMO as a result of the increased delocalization. The
MLCT chromophore also serves as an effective “exciton trap” in the PPE and
polythiophene systems, as the organic fluorescence is readily quenched after
chromophore incorporation and replaced by an MLCT-based emission.
2. The 2,2’-bipyridine subunits prevent complete delocalization in the n-
backbone and limit its effect of the observed photophysics. The same twisted bipyridine
subunits discussed above along with the biphenyl subunits limit the effective
delocalization of the PPE-type oligomers. This limit is observed in the lack of additional
red-shifting of the ground-state absorption spectra (Figure 3-2) or emission spectra
231

232
(Figure 3-3) of the 5-L oligomers and 5-Re complexes with increasing oligomer size.
This effect is most pronounced in the largest oligomer (5-Re-4), where both oligomer-
and metal-based transitions are observed, signifying isolation of multiple chromophores
in the same molecule. The monophenyl-based 5-LP oligomers and 5-ReP complexes,
however, do exhibit red-shifting absorption bands with increasing oligomer size, since
they do not have these same conjugation breaks. The 4-L oligomers and 4-Re complexes
also exhibit spectral red-shifting to a lesser degree, as the “bent” oligomer does not
appear to restrict the delocalization as effectively. This conclusion is further supported by
the semi-empirical calculations in chapter 5, which showed that “twisted” oligomers had
higher excited-state energies than planar analogues due to a restriction in possible 71-
delocalization.
3. An excited-state equilibrium exists between ligand- and metal-based states
( n,n* <-> MLCT) that control the observed photophysics. It is clear after our
experiments that the observed emission band for the PPE and polythiophene complexes is
a metal-based MLCT transition, while the transient absorption spectra is assigned to an
oligomer/polymer-based 37r,7i* transition. An equilibrium exists between these two
excited states, leading to the equivalent decay lifetimes for the two spectroscopic
techniques in the PPE and polythiophene (P4-Ru) systems. However, when the
equilibrium is disrupted by either changing the 3MLCT energy via ligand substitution in
the PPE oligomers or the 37i,n* energy via increasing the repeat unit length in the
polythiophenes, the decay lifetimes are dramatically altered. The 3MLCT emission decay
lifetime significantly decreases, while the 37r,7t* transient absorption decay lifetime
increases. Furthermore, when the variable temperature emission is examined in the PPE-

233
type oligomers, a transition between 3MLCT luminescence and 3n,n* phosphorescence is
observed. Both emissions are present at low temperature in the 5-Re and 5-ReP
complexes, while only phosphorescence is observed in the 4-Re complexes.
4. The structure and geometry of the oligomer/polymer exerts a dramatic effect
on the observed photophysics. As noted above, the monophenyl-based 5-LP/5-ReP
series exhibit different photophysics than the 5-L/5-Re series due to their inability to
attenuate delocalization. The monophenyl-based series also exhibits a slightly higher
'71,71* energy, as exhibited in the blue-shifted fluorescence spectra. The reason for this
energy difference is not clear. The alteration of the oligomer geometry from “linear”
5,5’-substitution to “bent” 4,4’-substitution in the 4-L/4-Re series brings altered
photophysics, including lower 37r,7t* energies and the presence of 3n,7t* phosphorescence
at reduced temperatures in both the oligomers and rhenium complexes as described
above. This difference is attributed to the differing dipole moments of the two oligomer
geometries, an altered excited state ordering that increases the (n —» 71*) nature of the 4-L
electronic transitions and possibly increased metal orbital mixing into the orbitals
involved in the optical transition. The repeat unit length increase in the polythiophenes
from P4-Ru to P6-Ru, as mentioned above, varies the 371,71* energy and precludes the
observation of 3MLCT luminescence by creating a more favorable non-radiative decay
pathway.
5. The oligomers and polymers exhibit properties favorable for materials
development. The PPE-type systems are fabricated into thin films with the Langmuir-
Blodgett technique and exhibit photophysical results similar to solution studies.
Furthermore, photoinduced energy transfer is observed both in solution and thin films

234
containing mixtures of the oligomer and MLCT complex, suggesting their potential use in
photonics applications. The thiophene polymers and model complexes exhibit oxidative
electron transfer to methyl viologen, illustrating their potential use in photonics and
supramolecular photochemistry. The polythiophenes could serve a dual role as both a
light harvesting complex and molecular wire in photosynthetic model systems, which is a
rare component in such designs.
6. The use of photothermal techniques can serve as a valuable aid in determining
excited-state energetics. The implementation of thermal lensing followed by
photoacoustic calorimetric techniques added an additional tool that, in conjunction with
other optical spectroscopic measurements, can obtain excited-state energies and/or yields.
While our results have definite flaws, this technique can be successfully utilized so long
as its limitations are kept in mind when the data is interpreted.
When the PPE-based oligomers are compared to their polymer counterparts, it is
clear that the oligomers are excellent models of their photophysical behavior. With this
research in mind, the focus can shift back to polymeric systems, and the knowledge
obtained in the oligomer research can be applied to better anticipate and interpret the
polymer photophysical results. The alteration of the MLCT chromophores and
oligomer/polymer structures exhibited above permits the controlled, predictable variation
of the observed photophysics, making these systems ideal foundations for constructing
more complex and novel Ti-conjugated polymer systems. The polythiophene research also
lays the groundwork for the incorporation of more novel, substituted MLCT
chromophores into the polythiophene backbone with the hope of boosting the materials
properties of these polymers, such as photoconductivity or non-linear optical effects.

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BIOGRAPHICAL SKETCH
Keith Walters was born in 1975 in Asheville, North Carolina, at the foot of the
Great Smoky Mountains, the only child of Marianne and Joe, an elementary school
teacher and professor of education at Western Carolina University. He spent his
childhood in nearby Waynesville, a quiet rural community of 6,000. Throughout his
youth, Keith was active in drama, playing such roles as Michael in Peter Pan, the Mad
Hatter in Alice in Wonderland, and the title roles in Oliver!, Willy Wonka and the
Chocolate Factory, and Dr. Doolittle. He also played the violin in the local youth
orchestra and solo handbells in his church. Keith was also involved in many academic
activities, including the math and science clubs and serving as the captain of the high
school quiz bowl team.
After graduating valedictorian of his senior class at Tuscola High School in 1993,
Keith attended Furman University in Greenville, South Carolina, where he received a
B.S. in chemistry in 1996. During his time in Greenville, Keith spent time in the labs of
his undergraduate mentor, Dr. Noel A.P. Kane-Maguire, and on the big couch at Coffee
Underground discussing chemistry and philosophy with other Furmanites. Somehow
between the two, he received the ACS outstanding senior award from the chemistry
department and graduated magna cum laude.
During his time at the University of Florida, Keith has expanded beyond his duties
in the lab to involve church activities. He is an active member of Trinity United
251

252
Methodist Church, where he has served on various musical committees and directs the
handbell choir. He still tries to do solo handbells when he has time. Upon graduation,
Keith will serve as a postdoctoral fellow for Dr. Joe Hupp at Northwestern University
with the ultimate goal of attaining an academic position somewhere in the south.

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 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.
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.
Daniel Talham
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.
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 Brenn
Associate Professor of Materials Science and
Engineering
This dissertation was submitted to the Graduate Faculty of the Department of Chemistry
in the College of Liberal Arts and Sciences and to the Graduate School and was accepted as
partial fulfillment of the requirements for the degree of Doctor of Philosophy.
August, 2000
Dean, Graduate School