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Conducting Polymers from Processable Precursors

and Their Applications to Gold Surfaces

Mustafa Selman Yavuz, Ph.D.

University of Connecticut, 2007

Abstract

Processability remains to be a significant hurdle towards the implementation

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of insoluble and infusible conducting polymers, which are synthesized by either

chemical (e.g. Lewis acid catalyzed via chemical oxidant (FeCh)) or


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electrochemical methods. Despite providing facile control in electrochemical

route, relatively poor yields have obviated electrochemical polymerization from


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being implemented on the industrial scale. Here, we have developed two

precursor routes that involve solid-state oxidative conversion to address the


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processing of solid forms of conductive polymers. The first route to CPs was

realized using tethered bis(3,4-ethylenedioxythiophene)thiophene (BEDOT-T)

and bis(3,4-ethylenedioxythiophene)benzene (BEDOT-B) off poly(norbornylene)

via Ring Opening Methathesis Polymerization (ROMP). Solid-state oxidative

conversion of these poly(norbornylene) backbones with pendant monomers

provides a crosslinked conductive network. The second route involves the

oxidative cleavage of silane units that are bound within a polymeric precursor

backbone containing conjugated BEDOT-B and BEDOT-T monomers. The solid-

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state oxidative conversion process involves the unzipping of the precursor and

the zipping of the conjugated conductive polymer to provide a linear polymer.

There has been significant interest in developing methods to prepare polymer

functionalized gold nanoparticles (AuNPs) and surfaces. Herein, we report the

use of surface-initiated ROMP for the preparation of BEDOT-T containing

polynorbornylene brushes on the gold surface and AuNPs, and their solid-state

oxidative conversion to conductive polymer networks. These polymer brushes

have been microscopically, electrochemically and spectroscopically

characterized. Reversibly tunable surface plasmon band of the gold

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nanoparticles is achieved by electrochemically switching between reduced and
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oxidized states of the conjugated polymer networks.
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Conducting Polymers from Processable Precursors

and Their Applications to Gold Surfaces

Mustafa Selman Yavuz, Ph.D.

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B.Sc., Bogazici University, 2001
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M.Sc., Worcester Polytechnic Institute, 2003
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A Dissertation

Submitted in Partial Fulfillment of the

Requirements for the Degree of

Doctor of Philosophy

At the

University of Connecticut

2007

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U M I N u m b e r: 3 3 0 0 6 4 7

IN FO R M A TIO N TO U SER S

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alignment can adversely affect reproduction.
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copyright material had to be removed, a note will indicate the deletion.


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APPROVAL PAGE

Doctor of Philosophy Dissertation

Conducting Polymers from Processable Precursors

and Their Applications to Gold Surfaces

Presented By

Mustafa Selman Yavuz, B.Sc., M.Sc.

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Major Advisor
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lory A. Sotzing

Associate Advisor
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fchael B. Smith

Associate Advisor

Amy Howell

University of Connecticut

2007

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LIST OF FIGURES

Figure Caption Page

1.1 Structures of some heterocyclic monomers 3

1.2 Organic-soluble alkyl-substituted poly(thiophene) 3

1.3 Three structural dyads of 3-alkylthiophene 5

1.4 PEDOT-PSSA dispersion in water, Baytron-P 12

1.5 Structure of D-sorbitol 12

1.6 The structure of A-carrageenan 14

1.7 A schematic diagram of surface-initiated ring opening 24

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metathesis polymerization IE
2.1 Schematic of a typical Teflon bodied EQCM cell, wherein, 38

the gold coated quartz crystals are held tightly between two
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rubber O-rings.

2.2 A schematic diagram of grazing-angle infrared 40

spectroscopy (GAIRS)
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3.1 A Oxidative electrochemical crosslinking of 8 67

3.1B Conventional electropolymerization of 3 68

3.1 C Cyclic voltammogram of 9 69

3.1 D Cyclic voltammogram of 7 70

3.2A Oxidative electrochemical crosslinking of 11 72

3.2B Conventional electropolymerization of 6 73

3.2C Cyclic voltammogram of 12 74

3.2D Cyclic voltammogram of 10 75

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Figure Caption Page

3.3A UV-Vis spectrum of 7 via conventional method 77

3.3B UV-Vis spectrum of 9 via solid-state oxidative crosslinking, 78

3.3C UV-Vis spectrum of 10 via conventional method 79

3.3D UV-Vis spectrum of 12 via solid-state oxidative crosslinking 80

3.4A Oxidative electrochemical crosslinking of 11 85

3.4B Cyclic voltammogram of 12 86

4.1 A Solid state oxidative electrochemical crosslinking of 101

poly(2a)

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4.1B Conventional electropolymerization of 1a
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4.1C Cyclic voltammogram of poly(3a) 103

4.1D Cyclic voltammogram of poly(1 a) 104


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4.2A Solid state oxidative electrochemical crosslinking of 106

poly(2b)

4.2B Conventional electropolymerization of 1b 107


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4.2C Cyclic voltammogram of poly(3b) 108

4.2D Cyclic voltammogram of poly(1b) 109

4.3A UV-Vis spectrum of poly(3a) via solid-state oxidative 111

crosslinking

4.3B UV-Vis spectrum of poly(1a) via conventional method 112

4.3C UV-Vis spectrum of poly(3b) via solid-state oxidative 113

crosslinking

4.3D UV-Vis spectrum of poly(1 b) via conventional method 114

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Figure Caption Page

4.4 Comparison scanning electron microscopy images of 116

conducting polymers from Solid-state oxidative conversion

and from Conventional electropolymerization

5.1 The structures of the molecules 1 and 2 126

5.2 The schematic diagram of surface-initiated ring opening 126

metathesis polymerization on gold surface

5.3 Scanning electron microscopy images of polymer brushes 127

on a Au-surface

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5.4 Cyclic voltammetry of polymer brushes on a Au-surface
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5.5 Atomic force microscopy images of polymer brushes on the 130

Au-surface
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5.6 FT-IR spectra of A) gold-surface after polymerization; B) 131

only poly(1); C) gold-surface before polymerization

6.1 The schematic diagram of surface-initiated ring opening 141


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metathesis polymerization on AuNPs

6.2 The structures of Grubbs' catalyst (1), initiating molecule 142

(2), the monomer (3), the polymers (poly(3), poly(4))

6.3 1HNMR spectrum of 2-functionalized AuNPs 144

6.4 The spectra of A) AuNPs functionalized with 2, B) 2- 145

modified AuNPs during the treatment of one equiv of 1, C)

2-modified AuNPs after the treatment of one equiv of 1

6.5 1HNMR spectrum of the AuNPs-poly(3) 147

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Figure Caption Page

6.6 Cyclic voltammetry of poly3-AuNPs 148

6.7 Transmission electron microscopy images of poly3-AuNPs 150

6.8 Atomic force microscopy images of A) AuNPs before 151

polymer growth and B) poly3-AuNPs

6.9 2 nm gold nanoparticles. UV spectra of 2-modified AuNPs; 152

poly3-AuNPs; reduced state of poly4-AuNPs; oxidized

state of poly4-AuNPs

6.10 7 nm gold nanoparticles. UV spectra of 2-modified AuNPs; 154

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poly3-AuNPs; reduced state of poly4-AuNPs; oxidized
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state of poly4-AuNPs
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LIST OF SCHEMES

Scheme Caption Page

1.1 Synthesis of poly(3-alkylthiophene) via Kumada coupling 5

1.2 Synthetic route to prepare regioregular poly(3- 7

alkylthiophene) via the McCullough method

1.3 Synthesis of regioregular poly(3-alkylthiophene) by the 8

Grignard method

1.4 Regioselective synthesis of poly(3-alkylthiophene) via 10

Rieke method

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1.5 Polymerization of thieno[3,4-b]thiophene to obtain a
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hypothetically networked polymer

1.6 Solid-state polymerization of dibromoEDOT 16


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2.1 Mechanistic diagram of electrochemical polymerization 43

2.2 Electrochemical desilylation polymerization mechanism 46

2.3 Mechanistic diagram of chemical polymerization 48


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3.1 Synthesis of 3 and 6 64

3.2 Ring-Opening Metathesis Polymerization of 3 and 6 65

4.1 Synthesis of poly(2a) and poly(2b), poly(3a) and poly(3b) 99

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LIST OF TABLES

Table Caption Page

3.1 The glass transition temperatures and 5% weight loss 83

decomposition temperatures of the polymers

4.1 Conductivities of polymers processed from precursors after 118

ferric chloride (FeCI3) oxidation and iodine (l2) doping.

4.2 The glass transition temperatures and 5% weight loss 118

temperatures of the polymers.

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TABLE OF CONTENTS

LIST OF FIGURES i

LIST OF SCHEMES v

LIST OF TABLES vi

CHAPTER 1. INTRODUCTION TO tt-CONJUGATED POLYMERS

1.1. tt-CONJUGATED POLYMERS 2

1.2. PROCESSABLE CONJUGATED POLYMERS: 4

1.3. GOLD NANOPARTICLES 15

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1.3.1. Plasmonic Gold Nanoparticles
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1.3.2. Surface Plasmons 17

1.3.3. Applications of Gold Nanoparticles 18


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1.4. POLYMER BRUSHES 19

1.4.1. Formation by Adsorption 20

1.4.2. Formation by Polymerization 22


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1.4.3. Surface Initiated Ring Opening Metathesis Polymerization 23

1.5. THESIS OF THIS WORK 26

1.6. REFERENCES 28

CHAPTER 2. INSTRUMENTATION, TECNIQUES, AND MECHANISMS

2.1. INSTRUMENTATION 34

2.2. TECHNIQUES 35

2.2.1. Cyclic Voltammetry 35

2.2.2. Electrochemical Quartz Crystal Microbalance (EQCM) 37

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2.2.3. Grazing Angle Infrared Spectroscopy (GAIRS) 39

2.2.4. Electrical Conductivity 41

2.3. MECHANISMS 41

2.3.1. Electrochemical Polymerization 41

2.3.2. Electrochemical Desilylation Polymerization 44

2.3.3. Chemical Polymerization 45

2.4. REFERENCES 49

CHAPTER 3. CONDUCTING POLYMER NETWORKS OF

POLY(NORBORNYLENE) CONTAINING ETHYLENEDIOXYTHIOPHENE

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(EDOT) MONOMERS via SOLID-STATE OXIDATIVE CROSSLINKING
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3.1. INTRODUCTION 52

3.2. EXPERIMENTAL 53
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3.2.1. Materials 53

3.2.2. Instrumentation 54

3.2.3. Electrochemistry 55
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3.2.4. Conductivity Measurements 56

3.2.5. Synthesis of 5-((2,5-dibromobenzyloxy)methyl) bicyclo[2.2.1] 57

hept-2-ene, endo/exo mixture (2)

3.2.6. Synthesis of 5-(3-(((bicyclo[2.2.1]hept-5-en-2-yl) 58

methoxy)methyl) -4-(2,3-dihydrothieno[3,4-b][1,4]dioxin-7-

yl)phenyl)-2,3-dihydrothieno [3,4-b][1,4] dioxine, endo/exo mixture

(3)

3.2.7. Synthesis of 8 59

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3.2.8. Preparation of 9 via Solid State Oxidative Crosslinking 60

3.2.9. Synthesis of endo & exo- 3-(((bicyclo[2.2.1]hept-5-en-2-


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yl)methoxy)methyl)-2,5-dibromothiophene (5)

3.2.10. Synthesis of endo & exo- 5-(4-(((bicyclo[2.2.1]hept-5-en-2- 61

yl)methoxy)methyl)-5-(2,3-dihydrothieno[3,4-b][1,4]dioxin-7-

yl) thiophen-2-yl)-2,3-dihydrothieno[3,4-b][1,4]dioxine (6)

3.2.11. Synthesis of 11 62

3.2.12. Preparation of 12 via Solid State Oxidative Crosslinking 62

3.3. RESULTS and DISCUSSIONS 63

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3.4. CONCLUSIONS IE 87

3.5. REFERENCES 87

CHAPTER 4. CONJUGATED POLYMERS OF BIS(3,4-ETHYLENEDIOXY


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THIOPHENE)-BASED MONOMERS FROM POLY(ARYLSILANE)

PRECURSORS via SOLID-STATE OXIDATIVE CONVERSION

4.1. INTRODUCTION 91
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4.2. EXPERIMENTAL 92

4.2.1. Materials 92

4.2.2. Instrumentation 93

4.2.3. Electrochemistry 94

4.2.4. Quartz Crystal Microbalance 95

4.2.5. Preparation of Scanning ElectronMicroscopy samples 95

4.2.6. Conductivity Measurements 95

4.2.7. General Procedure for Condensation Polymerizations 96

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4.2.8. Preparation of poly(3a) and poly(3b) via Solid State 97

Oxidative Conversion

4.2.9. Preparation of poly(1a) and poly(1b) via Conventional 98

Electrochemical Polymerization

4.3. RESULTS and DISCUSSIONS 98

4.4. CONCLUSIONS 119

4.5. REFERENCES 119

CHAPTER 5. CONJUGATED POLYMER BRUSHES via SURFACE-INITIATED

POLYMERIZATION ON A GOLD SURFACE

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5.1. INTRODUCTION IE 122

5.2. EXPERIMENTAL 123

5.2.1. Materials 123


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5.2.2. Instrumentation 124

5.2.3. Electrochemistry 124

5.3. RESULTS and DISCUSSIONS 125


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5.4.CONCLUSIONS 132

5.5. REFERENCES 132

CHAPTER 6. REVERSIBLY TUNABLE CONDUCTING POLYMER

FUNCTIONALIZED PLASMONIC GOLD NANOPARTICLES

6.1. INTRODUCTION 136

6.2. EXPERIMENTAL 137

6.2.1. Materials 137

6.2.2. Instrumentation 138

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6.2.3. Preparation and Characterization of Gold Nanoparticles 139

6.2.4. Polymer Growth on Gold Nanoparticles via Surface Initiated 140

Ring Opening Metathesis Polymerization

6.2.5. Electrochemistry 140

6.3. RESULTS and DISCUSSIONS 141

6.4. CONCLUSIONS 155

6.5. REFERENCES 155

APPENDICES. NUCLEAR MAGNETIC RESONANCE and THERMAL

ANALYSIS SPECTRA of MOLECULES

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A.1. 1H-NMR spectrum of 1 (Chapter 3)
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A.2. 1H-NMR spectrum of 2 (Chapter 3) 160

A.3. 1H-NMR spectrum of 5 (Chapter 3) 161


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A .4 .1H-NMR spectrum of 3 (Chapter 3) 162

A .5 .1H-NMR spectrum of 6 (Chapter 3) 163

A.6. 1H-NMR spectrum of 8 (Chapter 3) 164


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A.7. 1H-NMR spectrum of 11 (Chapter 3) 165

A .8 .1H-NMR spectrum of 2-modified gold nanoparticles (7nm) 166

(Chapter 6)

A .9 .1H-NMR spectrum of 2-modified gold nanoparticles (2nm) 167

(Chapter 6)

A. 1 0 .1H-NMR spectrum of poly3-gold nanoparticles (Chapter 6) 168

A.11 .13C-NMR spectrum of 1 (Chapter 3) 169

A. 12. 13C-NMR spectrum of 2 (Chapter 3) 170

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A. 1 3 .13C-NMR spectrum of 5 (Chapter 3) 171

A. 1 4 .13C-NMR spectrum of 3 (Chapter 3) 172

A.15 . 13C-NMR spectrum of 6 (Chapter 3) 173

A. 1 6 .13C-NMR spectrum of 8 (Chapter 3) 174

A.17. Thermal Gravimetric Analysis spectrum of 8 (Chapter 3) 175

A.18. Thermal Gravimetric Analysis spectrum of 11 (Chapter 3) 176

A.19. Thermal Gravimetric Analysis spectrum of poly(2b) (Chapter 4) 177

A.20. Thermal Gravimetric Analysis spectrum of poly(2a) (Chapter 4) 178

A.21. Thermal Gravimetric Analysis spectrum of poly(3b) (Chapter 4) 179

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A.22. Thermal Gravimetric Analysis spectrum of poly(3a) (Chapter 4)
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A.23. Thermal Gravimetric Analysis spectrum of 2-modified AuNPs 181

(Chapter 6)
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A.24. Thermal Gravimetric Analysis spectrum of 2-modified AuNPs 182

(Chapter 6)

A.25. Differential Scanning Calorimetry spectrum of 8 (Chapter 3) 183


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A.26. Differential Scanning Calorimetry spectrum of 11 (Chapter 3) 184

A.27. Differential Scanning Calorimetry spectrum of poly(2b) 185

(Chapter 4)

A.28. Differential Scanning Calorimetry spectrum of poly(2a) 186

(Chapter 4)

A.29. Differential Scanning Calorimetry spectrum of poly(3a) 187

(Chapter 4)

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CHAPTER 1
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INTRODUCTION TO tt-CONJUGATED POLYMERS


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1.1. tt-CONJUGATED POLYMERS:

Conjugated or conducting polymers (CPs) have a framework of alternating

single (a) and double (t t ) bonds. CPs are linear, branched, or crosslinked, having

TT-conjugation between repeat units. There have been tremendous research

efforts to make new CPs by both academia and industry after the discovery of

the unique properties of CPs by the Nobel Laureates in Chemistry for the year

2000, MacDiarmid, Shirakawa, and Heeger1. They discovered that iodine-doped

polyacetylene resulted in an increase in conductivity of several orders of

magnitude when compared to the undoped state. Since then, enormously

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different CPs has been made, mainly from basic heterocycles and their
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derivatives, such as pyrrole, thiophene, aniline, and furan, as shown in Figure

1.1 2.
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Electrical and optical properties of CPs can be changed via switching

between different redox states either chemically or electrochemically. Exceptional

flexibility, ease of processability, and low density make CPs attractive when
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compared to inorganic materials. Therefore, conducting materials based on

conjugated polymers have been applied in diverse areas such as biosensors,

high-storage capacitors, organic light emitting diodes (OLEDs), photovoltaics,

supercapacitors, solar cells, field effect transistors, molecular electronics, and

electrochromics 3.

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pyrrole thiophene furan aniline

Figure 1.1 Structures of some heterocyclic monomers

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Figure 1.2 Organic-soluble poly(3-hexylthiophene)

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1.2. PROCESSABLE CONJUGATED POLYMERS:

Conducting polymers (CPs) continue to attract scientists from different

disciplines due to their significant and varied applications. Despite their promising

features, poor processability due to insoluble and rigid backbones is the major

challenge for scientists.

Introducing flexible, long alkyl side chains into a monomer is one of the most

common approaches to overcome the poor processability of CPs, for instance

poly(3-hexylthiophene) as shown in Figure 1.2. These alkyl chains make the

polymers soluble in common organic solvents. Thus, the soluble CPs can be

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processed via spin, spray, or dip-coating, among other methods 4.
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The first soluble poly(3-alkylthiophene) was synthesized by Elsenbaumer et al.

via Kumada type coupling 5. As shown in Scheme 1.1, 2,5-diiiodo-3-


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alkylthiophene was treated with magnesium metal to form a Grignard reagent.

Following this, a nickel catalyst (NiBr2(dppp)) was added to prepare poly(3-

alkylthiohene).
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Sugimoto et al. also prepared poly(3-alkylthiophene) by oxidative chemical

polymerization using the chemical oxidant iron(lll) chloride (FeCh) 6. Due to the

ease of this polymerization, the chemical method became popular for the

preparation of poly(3-alkylthiophene)s. The resulting polymers from chemical

polymerization, however, have unavoidable defects because the 4-position of the

3-alkythiophene, (3 to sulfur atom, is also accessible for the polymerization.

These 3-defects block conjugation in the polymer chain.

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J fi 1) MgVTHF ^ jjk
2) Ni(dppp)Br2 < \ r T n

Scheme 1.1. Synthesis of poly(3-alkylthiophene) via Kumada coupling

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2, 2' (HH) 5, 5'(TT) 2, 5' (HT)

Figure 1.3. Three structural dyads of 3-alkylthiophene

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Since 3-alkylthiophene monomers are asymmetric, three types of dyad

structures (head-to-head (HH), head-to-tail (HT), and tail-to-tail (TT)) may form

during the polymerization when the monomers are coupled through the 2- and 5-

positions as shown in Figure 1.3.

Head-to-head couplings are unfavorable due to steric repulsion between both

of the alkyl chains with the lone pairs on the sulfur atoms 1. Polythiophenes that

contain a significant number of head-to-head couplings (which implies containing

tail-to-tail couplings) are referred to as regioirregular, while the polymers

containing only head-to-tail couplings are referred to as regioregular. In order to

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study and understand the importance of regioregularity, Elsenbaumer et al. had
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polymerized the 3-butyl-3methylbithiophene monomer and reported that the

conductivity of the polymer, which contains 63% head-to-tail orientation, is three


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times higher than the random copolymer of 3-butylthiophene and 3-

methylthiophene 8.

McCullough et al. carried out the first successful attempt to prepare


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regioregular poly(3-alkylthiohene) in 1992 9. They reported a method, referred to

as the McCullough method, for the synthesis of head-to-tail homogenous

coupling of 3-alkylthiophenes, the synthesis of which is shown in Scheme 1.2.

The resulting polymer shows a huge increase in the electrical conductivity in

comparison with regioirregular polymers.

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MgBr2,-40C

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NiCI2(dppp)
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Scheme 1.2 Synthetic route to prepare regioregular poly(3-alkylthiophene) via


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the McCullough method

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