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Abstract
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of insoluble and infusible conducting polymers, which are synthesized by either
processing of solid forms of conductive polymers. The first route to CPs was
oxidative cleavage of silane units that are bound within a polymeric precursor
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state oxidative conversion process involves the unzipping of the precursor and
polynorbornylene brushes on the gold surface and AuNPs, and their solid-state
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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
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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
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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In the unlikely event that the author did not send a complete manuscript
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APPROVAL PAGE
Presented By
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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
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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.
spectroscopy (GAIRS)
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Figure Caption Page
poly(2a)
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4.1B Conventional electropolymerization of 1a
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poly(2b)
crosslinking
crosslinking
ii
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Figure Caption Page
on a Au-surface
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5.4 Cyclic voltammetry of polymer brushes on a Au-surface
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Au-surface
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iii
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Figure Caption Page
state of poly4-AuNPs
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poly3-AuNPs; reduced state of poly4-AuNPs; oxidized
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state of poly4-AuNPs
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IV
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LIST OF SCHEMES
Grignard method
Rieke method
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1.5 Polymerization of thieno[3,4-b]thiophene to obtain a
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LIST OF TABLES
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TABLE OF CONTENTS
LIST OF FIGURES i
LIST OF SCHEMES v
LIST OF TABLES vi
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1.3.1. Plasmonic Gold Nanoparticles
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1.6. REFERENCES 28
2.1. INSTRUMENTATION 34
2.2. TECHNIQUES 35
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2.2.3. Grazing Angle Infrared Spectroscopy (GAIRS) 39
2.3. MECHANISMS 41
2.4. REFERENCES 49
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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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methoxy)methyl) -4-(2,3-dihydrothieno[3,4-b][1,4]dioxin-7-
(3)
3.2.7. Synthesis of 8 59
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3.2.8. Preparation of 9 via Solid State Oxidative Crosslinking 60
yl)methoxy)methyl)-5-(2,3-dihydrothieno[3,4-b][1,4]dioxin-7-
3.2.11. Synthesis of 11 62
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3.4. CONCLUSIONS IE 87
3.5. REFERENCES 87
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
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4.2.8. Preparation of poly(3a) and poly(3b) via Solid State 97
Oxidative Conversion
Electrochemical Polymerization
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5.1. INTRODUCTION IE 122
5.4.CONCLUSIONS 132
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6.2.3. Preparation and Characterization of Gold Nanoparticles 139
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A.1. 1H-NMR spectrum of 1 (Chapter 3)
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(Chapter 6)
(Chapter 6)
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A. 1 3 .13C-NMR spectrum of 5 (Chapter 3) 171
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A.22. Thermal Gravimetric Analysis spectrum of poly(3a) (Chapter 4)
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(Chapter 6)
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(Chapter 6)
(Chapter 4)
(Chapter 4)
(Chapter 4)
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CHAPTER 1
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1.1. tt-CONJUGATED POLYMERS:
single (a) and double (t t ) bonds. CPs are linear, branched, or crosslinked, having
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
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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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flexibility, ease of processability, and low density make CPs attractive when
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electrochromics 3.
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pyrrole thiophene furan aniline
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1.2. PROCESSABLE CONJUGATED POLYMERS:
disciplines due to their significant and varied applications. Despite their promising
features, poor processability due to insoluble and rigid backbones is the major
Introducing flexible, long alkyl side chains into a monomer is one of the most
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.
alkylthiohene).
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polymerization using the chemical oxidant iron(lll) chloride (FeCh) 6. Due to the
ease of this polymerization, the chemical method became popular for the
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J fi 1) MgVTHF ^ jjk
2) Ni(dppp)Br2 < \ r T n
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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-
of the alkyl chains with the lone pairs on the sulfur atoms 1. Polythiophenes that
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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
methylthiophene 8.
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MgBr2,-40C
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NiCI2(dppp)
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