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Donor-Acceptor Methods for Band Gap Control in Conjugated Polymers

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Title:
Donor-Acceptor Methods for Band Gap Control in Conjugated Polymers
Creator:
DUBOIS CHARLES J. ( Author, Primary )
Copyright Date:
2008

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Chlorides ( jstor )
Doping ( jstor )
Electrolytes ( jstor )
Macromolecules ( jstor )
Monomers ( jstor )
Oxidation ( jstor )
Patents ( jstor )
Polymers ( jstor )
Pyrazines ( jstor )
Voltammetry ( jstor )

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University of Florida
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University of Florida
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Copyright Charles J. Dubois. 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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8/1/2004
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71211498 ( OCLC )

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DONOR-ACCEPTOR METHODS FOR BAND GAP CONTROL IN CONJUGATED POLYMERS By CHARLES J. DUBOIS, JR. 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 2003

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To Sonya

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iii ACKNOWLEDGMENTS One of the hardest things to do is to properly recognize everyone that impacts your graduate career. Without a doubt, the most supportive person these last five years has been my wife, Sonya. Her unwavering patience and support have been the bedrock of our relationship. My parents, Charles and Rachel, have also been one of the biggest factors in my life. Their constant push for me to excel academically led to my choice of chemistry as a career. I would also like to thank Dr. John Reynolds, my research advisor, for his patience and support with my work at the University of Florida. Dr. Ken Wagener and Dr. Randy Duran have also been instrumental in completion of my degree. The help and guidance from Dr. Robin McCarley and Dr. Tracy McCarley during my undergraduate studies at LSU are greatly appreciated, especially in helping me choose a graduate school to further pursue my studies. A number of post-docs and fellow graduate students have also played an important role in my development as a chemist. Dr. Kyukwan Zong, Dr. Luis Madrigal, Dr. Shane Waybright, Dr. Jim Pawlow, and Dr. Hiep Ly have been post-docs that I have had the privileged to work with. It has been a pleasure to work with the following graduate students during my time here. Dr. Dean Welsh supplied early help with my project in addition to the interesting discussion of all things concerning Florida football. Dr. Carleton Gaupp assisted in much needed down to earth advice that always included a baseball analogy. Interesting discussion concerning the donor-acceptor compounds discussed in the work occurred every

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iv night with Dr. Chris Thomas over an icy, cold adult beverage. His perspectives on our field of work are greatly appreciated. Current graduate students must also be acknowledged for their role. John Sworen is thanked for his assistance with reactions, proofreading, CS, SWG, and knowing how to disassemble and reassemble any motor or other mechanical widget in the dark, blindfolded in under 30 seconds. The help from Tim Hopkins, Genay Jones, Ben Reeves, and Barry Thompson has also been highly valued. The support staff at the University has also been critical to the pursuit of my degree. Lorraine Williams has made sure that everything runs at peak efficiency in the Butler Polymer Laboratory and has always known the simplest way to fix the bureaucratic problems that crop up. Dr. James Deyrup and Lori Clark have also ensured that the students can focus on being students and have taken care of many of the problems that never reach our ears.

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v TABLE OF CONTENTS page ACKNOWLEDGMENTS ................................................................................................ iii LIST OF TABLES ............................................................................................................ vii LIST OF FIGURES ......................................................................................................... viii ABSTRACT xv CHAPTERS 1 INTRODUCTION ........................................................................................................... 1 1.1 A Brief History ................................................................................................. 1 1.2 Band Theory ..................................................................................................... 2 1.3 Optical Transitions and Doping Processes ....................................................... 4 1.4 Conductivity Processes ..................................................................................... 5 1.5 Structural Design and Synthetic Methodologies for Low Band Gap Materials ........................................................................................................... 6 1.6 Polymerization Methods ................................................................................. 10 1.7 Thesis of this Work .......................................................................................... 11 2 EXPERIMENTAL METHODS USED IN THE STUDY OF CONJUGATED . . POLYMERS .................................................................................................................. 13 2.1 Purification of Laboratory Chemicals ............................................................. 13 2.2 Electrochemical Methods ............................................................................... 15 2.2.1 Electrochemical Cells and Electrodes ..................................................... 15 2.2.2 Cyclic Voltammetry ................................................................................ 17 2.2.3 Differential Pulse Voltammetry .............................................................. 17 2.2.4 In-situ Conductivity ................................................................................ 18 2.3 Optical Methods .............................................................................................. 19 2.3.1 Spectroelectrochemistry .......................................................................... 19 2.3.2 Colorimetry ............................................................................................. 20 3 D-A-D MONOMER SYNTHESIS AND PROPERTIES ............................................. 22

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vi 3.1 Introduction ..................................................................................................... 22 3.2 Targeted Monomer Synthesis ......................................................................... 25 3.2.1 Donor Syntheses .................................................................................... 27 3.2.2 Acceptor Syntheses ................................................................................ 32 3.2.3 Donor-Acceptor-Donor Monomer Syntheses ........................................ 38 3.3 Monomer Structure and Properties ................................................................. 40 3.3.1 NMR ...................................................................................................... 40 3.3.2 X-ray Crystallography ........................................................................... 42 3.3.3 UV-Vis ................................................................................................... 43 3.3.4 Colorimetry ............................................................................................ 45 3.3.5 Electrochemistry .................................................................................... 46 3.4 Summary .......................................................................................................... 48 3.5 Experimental ................................................................................................... 49 3.5.1 General Methods .................................................................................... 49 3.5.2 Analytical Methods ................................................................................ 50 3.5.3 X-ray Crystallography ........................................................................... 50 3.5.4 Donor Synthesis ..................................................................................... 51 3.5.5 Acceptor Synthesis ................................................................................ 55 3.5.6 Donor-Acceptor Monomer Synthesis .................................................... 60 4 D-A-D POLYMER ELECTROCHEMISTRY AND OPTICAL PROPERTIES ........... 67 4.1 Introduction ..................................................................................................... 67 4.2 Electropolymerization ..................................................................................... 68 4.3 Polymer Cyclic Voltammetry .......................................................................... 74 4.4 Polymer Differential-Pulse Voltammetry ....................................................... 82 4.5 In-situ Conductivity ........................................................................................ 84 4.6 Polymer Spectroelectrochemistry ................................................................... 88 4.7 Polymer Colorimetry .................................................................................... 104 4.8 Summary and Discussion ............................................................................... 107 APPENDIX A SELECTED NMR AND UV-VIS DATA ................................................................... 113 B CRYSTALLOGRAPHIC INFORMATION FOR MONOMERS ............................... 137 C POLY(DIOXYTHIOPHENE) INTELLECTUAL PROPERTY ................................ 148 REFERENCES ............................................................................................................... 157 BIOGRAPHICAL SKETCH ........................................................................................... 193

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vii LIST OF TABLES Table page 4-1 Summary of electrochemical results and color swatches ..................................... 113 B-1 Atomic coordinates (x 10 4 ) and equivalent isotropic displacement parameters .......... ( 2 x 10 3 ) for BEDOT-PyrPyr-Ph 2 ...................................................................... 139 B-2 Bond lengths [] for BEDOT-PyrPyr-Ph 2 . .......................................................... 141 B-3 Bond angles[] for BEDOT-PyrPyr-Ph 2 . .............................................................. 143 B-4 Anisotropic displacement parameters ( 2 x 10 3 ) for BEDOT-PyrPyr-Ph 2 . ........ 145

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viii LIST OF FIGURES Figure page 1-1 Common conjugated polymers .................................................................................. 2 1-2 Band diagram of thiophene ...................................................................................... 4 1-3 Conductivities of various metals and conjugated polymers ...................................... 6 1-4 Evolution from PA to PEDOT-Pyr ............................................................................ 7 1-5 Planarity effects on band gap and the electrical and optical properties of conjugated .......... polymers .................................................................................................................... 9 1-6 Electrochemical polymerization mechanism ........................................................... 11 2-1 CIE 1931 coordinate ............................................................................................... 21 3-1 Reduction potentials of common nitrogen containing heterocycles ........................ 24 3-2 Donor-acceptor-donor XDOT-pyridine monomers targeted for synthesis .............. 26 3-3 Negishi and Stille coupling routes to BEDOT-pyridines. ....................................... 28 3-4 Preparation of Stille reagents for aryl-aryl cross-coupling reactions using palladium .......... catalysts. ................................................................................................................... 28 3-5 Preparation of ProDOT-Me 2 . .................................................................................. 31 3-6 Preparation of 3,4-dibromothiophene from bis-TMS thiophene ............................. 31 3-7 Preparation of pyrido[3,4b ]pyrazines from 3,4-diaminopyridine ......................... 32 3-8 Attempted preparation of 2,5-dibromopyrazine from 3-aminopyrazinoic acid ...... 35 3-9 Preparation of 5-bromo-pyrazin-2-ylamine with NBS from aminopyrazine .......... 35 3-10 Preparation of 3-fluoro-2,5-diiodopyrazine from chloropyrazine ........................... 36

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ix 3-11 Attempted preparation of 2,5-dichloropyrazine from chloropyrazine. ................... 38 3-12 Preparation of BEDOT-Pyridines. .......................................................................... 39 3-13 Preparation of BProDOT-Me 2 -Pyridines ............................................................... 39 3-14 Preparation of TMS-BEDOT-Pyridines ................................................................. 40 3-15 NMR aromatic chemical shifts of substituted pyridines ........................................ 41 3-16 Top and edge view of the crystal structure of BEDOT-PyrPyr-Ph 2 ...................... 44 3-17 UV-Vis of BXDOT-pyridines and their corresponding donor and acceptor .......... components in methylene chloride. ........................................................................ 45 3-18 UV-Vis of BXDOT-pyrido[3,4b ]pyrazines and their corresponding donor and .......... acceptor components in methylene chloride ............................................................ 46 3-19 Colorimetry of the BXDOT-pyridines in methylene chloride ............................... 47 3-20 Solution cyclic voltammetry of BEDOT-PyrPyr-Ph 2 , BProDOT-Me 2 -PyrPyr-Ph 2 , .......... and PyrPyr-Ph 2 ........................................................................................................ 48 4-1 3,4-Alkylenedioxythiophene-pyridine monomers fully characterized in this chapter..... ................................................................................................................. 68 4-2 3,4-Alkylenedioxythiophene-pyridine monomers studied in this chapter .............. 69 4-3 Cyclic voltammetric deposition of poly(1) (top) and poly(4) (bottom) at a scan rate .......... of 100 mV s -1 for 10 complete scans ....................................................................... 70 4-4 Cyclic voltammetric deposition of poly(9) (top) and poly(2) (bottom) at a scan rate .......... of 100 mV s -1 for 10 complete scans ....................................................................... 72 4-5 Attempted electrochemical polymerization of compound 7 at a scan rate of .......... 100 mV s -1 for 10 complete scans ........................................................................... 73 4-6 Cyclic voltammetry of pand n-type doping of poly(1), poly(4), and poly(2) in .......... monomer-free 0.1 M tetran -butylammonium perchlorate/acetonitrile solution at .......... 100 mV s -1 . .............................................................................................................. 75 4-7 Cyclic voltammetry of the n-type doping of poly(2) ............................................... 78 4-8 Cyclic voltammetry of poly(1) and poly(2) in four electrolyte systems: tetran .......... butylammonium perchlorate, tetran -ethylammonium perchlorate, sodium .......... perchlorate, and lithium perchlorate ........................................................................ 79

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x 4-9 Resonance behavior and potential charge stabilized reduction sites of poly(1) and .......... poly(2) ...................................................................................................................... 81 4-10 Differential-pulse voltammetry of poly(1) (top) and poly(2) (bottom) in tetra-n.......... butylammonium perchlorate, tetra-n-ethylammonium perchlorate, sodium .......... perchlorate, and lithium perchlorate (0.1 M perchlorate salt/acetonitrile) electrolyte .......... solutions ................................................................................................................... 83 4-11 In-situ conductance of poly(1) (red) and poly(2) (blue) in tetran -butylammonium .......... perchlorate (0.1 M perchlorate salt/acetonitrile) electrolyte solutions. ................... 86 4-12 In-situ conductance of the n-type doping region of poly(1) (top) and poly(2) (bottom) .......... in tetra-n-butylammonium perchlorate, tetra-n-ethylammonium perchlorate, sodium .......... perchlorate, and lithium perchlorate (0.1 M perchlorate salt/acetonitrile) electrolyte .......... solutions. .................................................................................................................. 87 4-13 UV-Vis-NIR spectrum of neutral poly(1), poly(2), poly(4), and poly(9) on an ITO.......... coated glass slide ..................................................................................................... 89 4-14 Spectroelectrochemistry of a film of poly(1) (top) on an ITO-coated glass slide .. 91 4-15 Spectroelectrochemistry of a film of poly(2) (top) on an ITO-coated glass slide .. 93 4-16 Spectroelectrochemistry of a film of poly(7) on an ITO-coated glass slide at various .......... applied potentials ..................................................................................................... 94 4-17 Poly(1) spectroelectrochemistry on an ITO-coated glass slide in monomer-free 0.1 .......... M tetran -butylammonium perchlorate/acetonitrile electrolyte solution ................. 95 4-18 Poly(1) spectroelectrochemistry on an ITO-coated glass slide in monomer-free 0.1 .......... M tetran -ethylammonium perchlorate/acetonitrile electrolyte solution ................. 96 4-19 Poly(1) spectroelectrochemistry on an ITO-coated glass slide in monomer-free 0.1 .......... M sodium perchlorate/acetonitrile electrolyte solution ........................................... 99 4-20 Poly(1) spectroelectrochemistry on an ITO-coated glass slide in monomer-free 0.1 .......... M lithium perchlorate/acetonitrile electrolyte solution ......................................... 100 4-21 Poly(2) spectroelectrochemistry on an ITO-coated glass slide in monomer-free 0.1 .......... M tetran -butylammonium perchlorate/acetonitrile electrolyte solution ............... 102 4-22 Poly(2) spectroelectrochemistry on an ITO-coated glass slide in monomer-free 0.1 .......... M tetran -ethylammonium perchlorate/acetonitrile electrolyte solution ............... 103 4-23 Poly(2) spectroelectrochemistry on an ITO-coated glass slide in monomer-free 0.1

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xi .......... M sodium perchlorate/acetonitrile electrolyte solution ......................................... 105 4-24 Poly(2) spectroelectrochemistry on an ITO-coated glass slide in monomer-free 0.1 .......... M litium perchlorate/acetonitrile electrolyte solution ........................................... 106 4-25 Colorimetry of films of poly(1), poly(2), and poly(9) on ITO-coated glass slides in .......... 0.1 M tetra-n-butylammonium perchlorate/acetonitrile solution ........................... 108 A-1 1 H NMR spectrum of (2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)-trimethyl .......... stannane in CDCl 3 ................................................................................................. 113 A-2 13 C NMR spectrum of (2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)-trimethyl.......... stannane in CDCl 3 ................................................................................................. 113 A-3 1 H NMR spectrum of trimethyl-(7-trimethylstannanyl-2,3-dihydro-thieno[3,4.......... b ][1,4]dioxin-5-yl)-silane in CDCl 3 ...................................................................... 114 A-4 1 H NMR spectrum of trimethyl-(7-trimethylstannanyl-2,3-dihydro-thieno[3,4.......... b ][1,4]dioxin-5-yl)-silane in CDCl 3 ...................................................................... 114 A-5 13 C NMR spectrum of 2,3,4,5-tetrabromothiophene in CDCl 3 ............................ 115 A-6 1 H NMR spectrum of 3,4-dibromothiophene in CDCl 3 ....................................... 116 A-7 13 C NMR spectrum of 3,4-dibromothiophene in CDCl 3 ...................................... 116 A-8 1 H NMR spectrum of 3,4-dimethoxythiophene in CDCl 3 ................................... 117 A-9 13 C NMR spectrum of 3,4-dimethoxythiophene in CDCl 3 .................................. 117 A-10 1 H NMR spectrum of 3,3-dimethyl-3,4-dihydro-2H-thieno[3,4b ][1,4]dioxepine in ........... CDCl 3 ................................................................................................................... 118 A-11 13 C NMR spectrum of 3,3-dimethyl-3,4-dihydro-2H-thieno[3,4b ][1,4]dioxepine ......... .. in CDCl 3 118 A-12 1 H NMR spectrum of 2,5-bis-trimethylsilanyl-thiophene in CDCl 3 .................. 119 A-13 13 C NMR spectrum of 2,5-bis-trimethylsilanyl-thiophene in CDCl 3 ................ 119 A-14 1 H NMR spectrum of 2,3-diphenyl-pyrido[3,4b ]pyrazine in CDCl 3 ................ 120 A-15 13 C NMR spectrum of 2,3-diphenyl-pyrido[3,4b ]pyrazine in CDCl 3 .............. 120 A-16 1 H NMR spectrum of 2,5-dibromopyridine-3,4-diamine in DMSOd 6 . ............ 121

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xii A-17 13 C NMR spectrum of 2,5-dibromopyridine-3,4-diamine in DMSOd 6 . ........... 121 A-18 1 H NMR spectrum of 5,8-dibromo-2,3-diphenyl-pyrido[3,4b ]pyrazine ............ 122 A-19 13 C NMR spectrum of 5,8-dibromo-2,3-diphenyl-pyrido[3,4b ]pyrazine .......... 122 A-20 1 H NMR spectrum of 3-amino-pyrazine-2-carboxylic acid methyl ester ........... 123 A-21 13 C NMR spectrum of 3-amino-pyrazine-2-carboxylic acid methyl ester .......... 124 A-22 1 H NMR spectrum of 3-amino-6-bromo-pyrazine-2-carboxylic acid ................. 124 A-23 13 C NMR spectrum of 3-amino-6-bromo-pyrazine-2-carboxylic acid ................ 125 A-24 1 H NMR spectrum of 5-bromo-pyrazine-2-ylamine in CDCl 3 ........................... 126 A-25 13 C NMR spectrum of 5-bromo-pyrazine-2-ylamine in CDCl 3 .......................... 126 A-26 1 H NMR spectrum of 3-chloropyrazine-1-oxide in CDCl 3 ................................. 127 A-27 13 C NMR spectrum of 3-chloropyrazine-1-oxide in CDCl 3 ............................... 127 A-28 1 H NMR spectrum of 2,5-bis-(2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)........... pyridine in CDCl 3 .. ............................................................................................... 128 A-29 13 C NMR spectrum of 2,5-bis-(2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)-pyridine ........... in CDCl 3 . ............................................................................................................. 128 A-30 UV-Vis spectrum of 64 mM 2,5-bis-(2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)........... pyridine in methylene chloride ............................................................................. 129 A-31 1 H NMR spectrum of 5,8-bis-(2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)........... pyrido[3,4b ]pyrazine in CDCl 3 ........................................................................... 130 A-32 1 H NMR spectrum of 5,8-bis(2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)-2,3........... diphenyl-pyrido[3,4b ]pyrazine in CDCl 3 ............................................................ 131 A-33 13 C NMR spectrum 5,8-bis(2,3-dihydro-thieno[3,4-b][1,4]dioxin-5-yl)-2,3........... diphenyl-pyrido[3,4b ]pyrazine in CDCl 3 ............................................................ 131 A-34 UV-Vis spectrum of 1.8 mM 5,8-bis(2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)........... 2,3-diphenyl-pyrido[3,4b ]pyrazine in methylene chloride .................................. 132 A-35 1 H NMR spectrum of 2,5-bis-(3,3-dimethyl-3,4-dihydro-2 H -thieno[3,4........... b ][1,4]dioxepin-6-yl)-pyridine in CDCl 3 .............................................................. 133

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xiii A-36 13 C NMR spectrum of 2,5-bis-(3,3-dimethyl-3,4-dihydro-2 H -thieno[3,4........... b ][1,4]dioxepin-6-yl)-pyridine in CDCl 3 .............................................................. 134 A-37 UV-Vis spectrum of 2.8 mM 2,5-bis-(3,3-dimethyl-3,4-dihydro-2 H -thieno[3,4........... b ][1,4]dioxepin-6-yl)-pyridine in methylene chloride .......................................... 135 A-38 1 H NMR spectrum of 5,8-bis-(3,3-dimethyl-3,4-dihydro-2 H -thieno[3,4........... b ][1,4]dioxepine-6-yl)-2,3-diphenyl-pyrido[3,4b ]pyrazine in CDCl 3 ................ 136 A-39 13 C NMR spectrum of 5,8-bis-(3,3-dimethyl-3,4-dihydro-2 H -thieno[3,4........... b ][1,4]dioxepine-6-yl)-2,3-diphenyl-pyrido[3,4b ]pyrazine in CDCl 3 ................ 136 B-1 Crystal data and structure refinement for BEDOT-PyrPyr-Ph 2 ............................ 137

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xiv Abstract of Dissertation Presented to the Graduate School of the University of Florida in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy DONOR-ACCEPTOR METHODS FOR BAND GAP CONTROL IN CONJUGATED POLYMERS By Charles Joseph DuBois Jr. December 2003 Chair: John R. Reynolds Major Department: Chemistry A family of alternating bis -3,4-ethylenedioxythiophene (bi-EDOT) and functionalized pyridine donor-acceptor conjugated polymers have been prepared via electropolymerization of donor-acceptor-donor (D-A-D) monomers. The use of this alternating donor-acceptor strategy allows for the synthesis of low band gap polymers in which the redox, electronic, and optical properties are controlled through easily approachable synthetic modification of the polymer backbone. This control allows "fine-tuning" of the band gap to values between 1.2 and 1.9 eV by making slight structural changes. These structural manipulations yield varied electronic absorption energies for a range of colors in the neutral polymer films, multi-colored electrochromism, and accessible states for reduction leading to n-type doping. The polymers prepared have been characterized using cyclic voltammetry, differential pulse voltammetry, in-situ conductance, colorimetry, and UV-Vis-NIR spectroscopy demonstrating that the polymers can undergo both pand n-type doping and color

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xv changes in both redox states. The parent polymer, poly(2,5-bis-(2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)-pyridine) (PBEDOT-Pyr), has four accessible color states: an oxidized dark blue, a neutral red, a reduced sky-blue, and a protonated dark blue. It has a band gap of 1.9 eV with a peak oxidation occuring near +1.1 V and peak reduction at -1.6 V vs SCE. A pyridopyrazine-based polymer, poly(5,8-bis-(2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)-2,3-diphenyl-pyrido[3,4b ]pyrazine) (PBEDOT-PyrPyr(Ph) 2 ), also undergoes color changes upon doping. Incorporation of the stronger acceptor relative to the pyridine lowers the band gap to 1.2 eV, while the oxidation potential is only lowered slightly to +0.8 V. Peak reduction potentials are centered at -1.1 V and -1.7 V. A shift in reduction potential values to near -1.0 V allows for n-type doping to occur on the benchtop rather than in an argon-filled drybox. The effect of various perchlorate electrolytes (tetran -butylammonium, tetran -ethylammonium, sodium, and lithium) on both the pand n-doping of the polymer has also been studied. Conductivity measurements show that, for both the pyridine and pyrido[3,4b ]pyrazine acceptors, n-type doping conductivities are within an order of magnitude of ptype doping conductivities, which is the smallest p-type/n-type conductance ratio reported for a polyheterocycle of this type to date. Reductive spectroelectrochemistry performed on these two systems shows that n-type doping only occurs when TBA + and TEA + are used as counter ions. When Na + and Li + are used as counter ions, color changes do occur, but no evidence of charge carrier formation is seen, indicating that reduction is not a doping process with these two electrolytes.

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1 CHAPTER 1 INTRODUCTION 1.1 A Brief History The initial focussed study of conjugated polymers originated in the late 1970’s with the discovery that polyacetylene could become highly conducting when chemically doped. 1 Further research has led to the study of other p -conjugated polymers, such as polythiophenes and polypyrroles, among others, as shown in Figure 1-1. 2 Early work in this field held the hope that these types of polymer systems would serve as replacements for highly conductive metals, such as copper and aluminum for electrical transport or battery electrodes. However, due to the instability of these systems when highly doped, other more practical uses have been realized such as thin film transistors, 3 a sensors, 3b-c polymer light1. Chiang, C. K.; Park, Y. W.; Heeger, A. J.; Shirakawa, H.; Louis, E. J.; MacDiarmid, A. G. Phys. Rev. Lett. 1977 , 39 , 1098-1101. 2. (a) Chan, H. S. O.; Ng, S. C. Prog. Polym. Sci. 1998 , 23 , 1167-1231. (b) Groenendaal, L.; Jonas, F.; Freitag, D.; Pielartzik, H.; Reynolds, J. R. Adv. Mater. 2000 , 12 , 481494. (c) McCullough, R. D. Adv. Mater. 1998 , 10 , 93-116. (d) Roncali, J. Chem. Rev. 1992 , 92 , 711-738. 3. (a) Halls, J. J. M.; Walsh, C. A.; Greenham, N. C. ; Marseglia, E. A.; Friend, R. H. ; Moratti, S. C. ; Holmes, A. B. Nature 1995 , 376 , 498. (b) Albert, K. J.; Lewis, N. S.; Schauer, C. L.; Sotzing, G. A.; Stitzel, S. E.; Vaid, T. P.; Walt, D. R. Chem. Rev. 2000 , 100 , 2595-2626. (c) McQuade, D. T.; Pullen, A. E.; Swager, T. M. Chem. Rev. 2000 , 100 , 2537-2574. (f) Kraft, A.; Grimsdale, A. C.; Holmes, A. B. Angew. Chem. Int. Ed. 1998 , 37 , 402-428. (e) Brabec, C. J.; Sariciftci, N. S.; Hummelen, J. C. Adv. Funct. Mater. 2001 , 1 , 15-26. (f) For a review of this field see Electrochimica Acta 2001 , 46 , issue 13-14.

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2 emitting diodes, 3d photovoltaics, 3e and electrochromic devices. 3f A comprehensive list of US Patents based on dioxythiophene applications can be found in Appendix C. As a result of the discovery that polyacetylene could be made highly conductive, Heeger, MacDiarmid, and Shirakawa were awarded the 2000 Nobel Prize in Chemistry. In order to tune the specific properties desired for end use applications, more complicated monomers are needed that manipulate both the electronic and optical properties of the polymer systems. To successfully design these systems, a basic understanding of the material properties is needed and is described in subsequent sections. Dissertations from the Reynolds research group give excellent overviews of band theory, optical transitions and doping, conductivity, and low band gap polymers and serve as the background that this dissertation is built upon. 4 Here, fundamentals of conjugated polymer background information are offered along with a brief discussion of the various techniques used for preparation of low band gap materials. 1.2 Band Theory By linking a string of p aromatic molecules together, conjugated systems can be created such that the HOMO and LUMO of these extended systems merge into continuous Figure 1-1. Common conjugated polymers 4. (a) Gaupp, C. L. Structure-Property Relationships of Electrochromic 3,4-Alkylenedioxyheterocycle-Based Polymers and Copolymers. Ph. D. Dissertation, University of Florida, Gainesville, FL, 2002. (b) Thomas, C. T. Donor-Acceptor Methods for Band Gap Reduction in Conjugated Polymers: The Role of Electron Rich Donor Heterocycles. Ph. D. Dissertation, University of Florida, Gainesville, FL, 2002.

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3 bands that can be modeled as semiconductors. By taking the E 1/2 values for oxidation for thiophene oligomers and their onset of absorption from UV-Vis experiments, a plot of the position of the HOMO and LUMO can be analyzed as shown in Figure 1-2. 5 Thiophene oxidizes at 2.07 V vs SCE and has a HOMO-LUMO separation of 5.0 eV based on UV-Vis experiments. Addition of a second thiophene ring to create bithiophene extends the conjugation and results in a lowering of both the energy gap and oxidation potential to 3.5 eV and 1.31 V, respectively. 6 Terthiophene has an oxidation potential of 1.05 V and an energy gap of 3.0 eV. 7 The oxidation of quaterthiophene occurs at 0.95 V, and its energy gap is 2.8 eV. 8 As the p -system is extended further to sexithiophene, the values approach a saturation point with oxidation occuring at 0.83 V and an energy gap of 2.5 eV. 9 Further extension leads to intractable solids and, at this point, the addition of thiophenes results in properties that are “polythiophene-like.” Polythiophene oxidizes at 0.7 V, and its energy gap is 2.0 eV. 5. Streitwieser, A., Jr. Molecular Orbital Theory for Organic Chemists , Wiley: New York, 1961. 6. Chadwick, J. E.; Kohler, B. E. J. Phys. Chem. 1994 , 98 , 3631-3637 7. (a) DiCsare, N.; Bellette, M.; Marrano, C.; Leclerc, M.; Durocher, G. J. Phys. Chem. A 1999 , 103 , 795-802. (b) Roncali, J.; Gorgues, A.; Jubault, M. Chem. Mater. 1993 , 5 , 1456-1464 8. DiCsare, N.; Bellette, M.; Garcia, E. R.; Leclerc, M. J. Phys. Chem. A 1999 , 103 , 3864-3875 9. Loi, M. A.; Martin, C.; Chandrasekhar, H. R.; Chandrasekhar, M.; Graupner, W.; Garnier, F.; Mura, A.; Bongiovanni, G. Phys. Rev. B 2002 , 66 , 113102

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4 1.3 Optical Transitions and Doping Processes As conjugated polymers are insulating or poorly conducting due to their energy gaps, only through doping can these systems become highly conductive allowing for new optical transitions to be seen. There are four classes of conductivity: metals, semimetal, semiconductor, and insulator. Metals are the most familiar and have no band gap due to their band being half-filled. Semi-metals consist of overlapping orbitals that create a partially filled band which allows for conduction processes to occur. Neutral polyheterocycles are either semi-conducting or insulating, depending on their band gap magnitude. A semi-conductor is considered to have a gap less than 3 eV but is nonFigure 1-2. Band diagram of thiophene

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5 conducting. An insulator is any material such as poly(ethylene terephthalate) with a band gap greater than 3 eV. As shown in Figure 1-3, doping induces conductivity changes in polyacetylene on the order of 10 8 -10 9 . Comparable changes are seen with polypyrrole, polythiophene, and poly(phenylenevinylene). 10 1.4 Conductivity Processes There are three main charge transport processes associated with materials: metallic, redox, and ionic. Ionic conductivity involves movement of ions in an electric field. Nafion is an example of a material that displays ionic conductivity. Redox conductivity involves the exchange of electrons in a mixed valence metal-ligand system. Electrons are exchanged through a hopping mechanism between adjacent redox centers. As will be discussed in chapter 4, the majority of polymers that are capable of reduction display redox conductivity. 10. Adapted from Menon, R.; Yoon, C. O.; Moses, D.; Heeger, A. J. Handbook of Conducting Polymers, 2nd Ed. T. A. Skotheim, R L. Elsenbaumer, J. R. Reynolds, Eds. Marcel Dekker: New York, 1998. Data for the conjugated polymers was taken from the following references (i) PPy-PF 6 : (a) Hagiwara, T.; Hirasaka, M.; Sato, K.; Yamaura, M. Synth. Met. 1990 , 36 , 241. (b) Sato, K.; Yamaura, M.; Hagiwara, T.; Murata, K.; Tokumoto, M. Synth. Met. 1991 , 40 , 35. (c) Yoon, C. O.; Reghu, M.; Moses, D.; Heeger, A. J. Phys. Rev. B 1994 , 49 , 10851. (ii) PA-I: (a) Tsukamoto J. Adv. Phys. 1992 , 41 , 509. (b) Reghu, M.; Vakiparta, K.; Cao, Y.; Moses, D. Phys. Rev. B 1994 , 49 , 16162. (c) Yoon, C. O.; Reghu, M.; Heeger, A. J.; Park, E. B.; Park, Y. W.; Akagi, K.; Shirakawa, H. Synth. Met. 1995 , 69 , 79.; (d) Nogami, Y.; Kaneko, H.; Ito, H.; Ishiguro, T.; Sasaki, T.; Toyota, N.; Takahashi, A.; Tsukamoto, J. Phys. Rev. B 1991 , 43 , 11829. (e) Nogami, Y.; Kaneko, H.; Ishiguro, T.; Takahashi, A.; Tsukamoto, J.; Hosoito, N. Solid State Commun. 1990 , 76 , 583 (f) Kaneko, H.; Ishiguro, T. Synth. Met. 1994 , 65 , 141. (g) Shirikawa, H.; Zhang, Y. X.; Okuda, T.; Sakamaki, K.; Akagi, K. Synth. Met . 1994 , 65 , 93. (iii) PANI-CSA: Yang, C. S.; Cao, Y.; Smith, P.; Heeger, A. J. Synth. Met. 1993 , 53 , 293. (iv) PPV-HSO 4 : Ohnishi, T.; Noguchi, T.; Nakano, T.; Hirooka, M.; Murase, I. Synth. Met. 1991 , 41-43 , 309. (v) P3HT-X: Yoon, C. O.; Reghu, M.; Moses, D.; Heeger, A. J.; Cao, Y.; Chen, T.-A.; Wu, X.; Rieke, R. D. Synth. Met. 1995 , 75 , 229.

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6 As discussed earlier, in order for a polyheterocycle to exhibit metallic conductivity, it must be highly doped. Intermediate doping results in charge carriers called polarons. Polarons have an unpaired spin, and they are radical cations or radical anions. They exhibit an EPR signal and are delocalized over four to five heterocycle rings. High doping levels result in formation of spinless dication bipolarons. 1.5 Structural Design and Synthetic Methodologies for Low Band Gap Materials In order to functionalize a polymer to have the desired electrochemical and optical properties, both the valence and conduction energies can be controlled by the energy gap Figure 1-3. Conductivities of various metals and conjugated polymers. Adapted from reference 10.

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7 (the relation of the energy levels to one another) or the position of the energies (oxidation or reduction potentials) and has been thoroughly reviewed. 11 As shown in Figure 1-4, evolution of the polymer systems from polyacetylene to poly(BEDOT-Pyr), a polymer discussed in more detail in chapter 4, shows the effects of heteroatom placement and position of the double bond on band gap and thus color. Low band gap materials will ultimately provide a means for stable n-doped states on the benchtop and highly intrinsically conducting polymer systems. 11. Roncali, J. Chem. Rev. 1997 , 97 , 173-205 Figure 1-4. Evolution from PA to PEDOT-Pyr

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8 In designing low band gap systems, there are a variety of methodologies that can be used to achieve polymers with band gaps less then 2 eV. Five basic approaches have been used to reduce band gap that include controlling bond-length alternation (Peierls distortion), creating highly planar systems, inducing order by interchain effects, resonance effects along the polymer backbone, and using donor-acceptor effects. Bond-length alternation is the difference in length of the single and double bond along the polyheterocycles backbone. Of these states, the quinoidal form has a much lower band gap than the aromatic state. The classical example of aromaticity control in conjugated polyheterocylces is polyisothianaphthene, a polythiophene with a benzene ring fused at the 3and 4-positions along the polymer backbone. Benzene, with an energy of aromatization of 1.56 eV, is more aromatic than thiophene (1.26 eV). This forces PITN to be more energetically stable in the quinoidal state, which provides for a lowered band gap of 1.1 eV compared to polythiophenes band gap of 2.0 eV. As shown in Figure 1-5, the higher the torsional angle between adjacent rings the larger the band gap of a system. A number of groups have used different methods to achieve highly planar low band gap systems. One successful approach has been ladder-type polymers such as the polyacene family. Another has been synthesis of polyquinoxalines. However, these systems exhibit extreme cases of bond-length alternation and give much higher energy gaps then expected. The strongest example of the influence between polymer chains is poly(3hexylthiophene). Regioregular poly(3-alkylthiophene)s have been prepared that show much lower band gaps and better electrochemical properties due to the ordering of the polymer films.

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9 A more recent example of aromaticity effects are the thienylS , S -dioxide family of systems. Oxidation of the sulfur on thiophene prevents its lone pair contribution to the rings aromaticity, in effect making it a “pinned” cis-transiod polyacetylene. Copolymers with thiophene give band gaps of 1.5 eV and reduction potentials with E 1/2 values of -1.1 V vs SCE. 12 Figure 1-5. Planarity effects on band gap and the electrical and optical properties of conjugated polymers. Adapted from reference 14 12. (a) Arbizzani, C.; Mastragostino, M.; Soavi, F. Electrochim. Acta 2000 , 45 , 22732278. (b) Barbarella, G.; Favaretto, L.; Sotgiu, G.; Zambianchi, M.; Arbizzani, C.; Bongini, A.; Mastragostino, M. Chem. Mater. 1999 , 11 , 2533-2541. (c) Bongini, A.; Barbarella, G.; Favaretto, L.; Zambianchi, M.; Mastragostino, M.; Arbizzani, C.; Soav, F. Synth. Met. 1999 , 101 , 13-14. (d) Suh, M. C.; Jiang, B.; Tilley, T. D. Angew. Chem. Int. Ed. 2000 , 39 , 2870-2873

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10 Work in this dissertation involves manipulation of donor-acceptor effects such that control of the band gap and relative position of the valence and conduction bands yield desired results. In this technique, a donor molecule is chosen such that its valence band is at an energy level or oxidation potential for the properties desired. An acceptor molecule is then chosen such that its reduction potential or position in energy space is where the organic polymer chemists desires. By coupling these systems in a 1:1 ratio alternatingly across the polymer backbone, the polymer has the valence band of the donor and the conduction band of the acceptor. This results in the phenomenon known as “band gap compression.” The hybridized system has the properties of the parents. This approach has been the most effective for low band gap materials and has been extensively reviewed. 13 1.6 Polymerization Methods Electrochemical polymerization is the method of choice for rapid characterization of conjugated polymers. Whether using cyclic, potentiostatic, or galvanostatic methods, electrochemical polymerization allows for synthesis of the desired polymer on an electrode’s surface that allows for both electrochemical and optical studies. As shown in Figure 1-6, EDOT is converted to its radical cation by removal of an electron under an applied electric field. This intermediate is stabilized by the ethylenedioxy pendant group. Two reactions can then occur – attack of the radical cation on a neutral monomer or coupling of two radical cations. Both routes yield an intermediate that is rearomatized upon loss of two protons to give a dimer unit. Repeated coupling results in synthesis of the polymer. 13. van Mullekom, H. A. M.; Vekemans, J. A. J. M.; Havinga, E. E.; Meijer, E. W. Mater. Sci., Eng., R 2001 , 32 , 1-40

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11 1.7 Thesis of This Work This chapter discussed the beginnings of conjugated polymers research and laid the fundamental understanding of their properties as semiconductors. Chapter 2 will offer a brief discussion on the electrochemical and optical experimental techniques, such as cyclic voltammetry, differential pulse voltammetry, and in-situ conductance, that were used in the body of this work for characterization of the monomers and polymers detailed in subsequent chapters. The synthesis and analytical characterization of the pyridine and pyrido[3,4b ]pyrazine D-A-D monomers are detailed in chapter 3. Polymer synthesis and study of the electrochemical and optical properties of n-type dopable systems are discussed Figure 1-6. Electrochemical polymerization mechanism

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12 in chapter 4. Unique electrolyte effects associated with the reduced state of the polymers are closely examined to offer an explanation for their poor properties.

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13 CHAPTER 2 EXPERIMENTAL METHODS USED IN THE STUDY OF CONJUGATED POLYMERS This chapter serves as an overview of general experimental techniques and material preparation used in the synthesis (chapter 3) and characterization (chapter 4) of conjugated polymers. Conjugated polymer research is an ever evolving discipline of polymer science that requires modification of traditional techniques for each system to be studied. Organic polymer chemists require a knowledge of a broad array of techniques due to the need to not only prepare the material to be studied but also to fully characterize it using physical, analytical, and materials science methodologies. Prior dissertations from the Reynolds research group give excellent general experimental overviews. Here, experimental considerations and detals specifically to the work presented here are given. 1 2.1 Purification of Laboratory Chemicals All the electrochemical work described here was performed in an argon-filled dry box or on the bench top under an argon blanket due to the reactivity of the conjugated polymers studied when reduced as they are designed to be easily oxidized. Due to the high 1. (a) Gaupp, C. L. Structure-Property Relationships of Electrochromic 3,4-Alkylenedioxyheterocycle-Based Polymers and Copolymers. Ph. D. Dissertation, University of Florida, Gainesville, FL, 2002. (b) Thomas, C. T. Donor-Acceptor Methods for Band Gap Reduction in Conjugated Polymers: The Role of Electron Rich Donor Heterocycles. Ph. D. Dissertation, University of Florida, Gainesville, FL, 2002.

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14 reactivity of this redox state, it is exceedingly important that all solvents and electrolytes are adequately dried and de-oxygenated before performing experiments. Acetonitrile was used exclusively as an electrochemical solvent. As discussed in chapter 4, other common electrochemical solvents such as propylene carbonate led to no polymer deposition when oxidative potentials were applied. A typical procedure was as follows. Acetonitrile (500 mL) was distilled from calcium hydride into a 1 L Schlenk flask that had been previously flame dried. Next, the solvent was degassed by a freeze-pumpthaw process. The sealed flask was placed in a liquid nitrogen filled dewar. After the acetonitrile solidified, the flask was exposed to vacuum for 30 minutes. The flask was then sealed again, the liquid nitrogen was removed, and the acetonitrile was allowed to melt. This process was then repeated two more times and, subsequently, the solvent placed into the dry box. Activated molecular sieves (3) were added to the solvent to remove any residual water. Purification of methylene chloride, which was added to the acetonitrile in small amounts to allow for complete monomer dissolution, was purified using the same procedure. Adequate purification of electrolytes is also important for obtaining the best electrochemical results. Tetran -butylammonium perchlorate (TBAP) and tetran ethylammonium perchlorate (TEAP) were synthesized by the metathesis reaction of the appropriate n -alkylammonium bromide dissolved in a minimal amount of water and perchloric acid. The resulting precipitate was filtered and washed with copious amounts of water. It is extremely important to remove any residual perchloric acid at this point in order to minimize the number of recrystallizations when purifying. The electrolyte was then recrystallized twice from i -propanol to give white plates. In order to completely dry the

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15 electrolyte, it was placed in a round bottom flask and heated under vacuum for 48 hours. The flask was backfilled with argon, sealed, and placed in the dry box. Sodium and lithium perchlorate were each placed in a Schlenk tube and placed under vacuum. A blast shield was then placed in front of the tube and it was heated until the electrolyte melted. After cooling under vacuum, the tube was backfilled with argon and placed in the dry box. 2.2 Electrochemical Methods A number of electrochemical characterization methods used for the study of conjugated polymers are at the disposal of the organic polymer chemist. The most general method used has been cyclic voltammetry. It allows for a means to study redox states of the polymer, discern E 1/2 values, and study redox switching kinetics by varying the scan rate of the experiment. This section will then detail fundamentals of cyclic voltammetry and two other electrochemical techniques used in this body of work: differential pulse voltammetry and in-situ conductivity. It will also describe electrochemical cell considerations and reference electrodes. An extensive review of electrochemical techniques and their application to conjugated polymers can be found elsewhere. 2 2.2.1 Electrochemical Cells and Electrodes Electrochemical experiments described in this body of work used either an EG&G Princeton Applied Research Model 273A potentiostat/galvanostat for cyclic and differential pulse voltammetry, or an EG&G Princeton Applied Research Model 273A potentiostat/galvanostat in tandem with a Pine Bipotentiostat Model AFCBP1 for in-situ conductivity experiments. A three-electrode cell configuration was used that consisted of 2. Doblhofer, K.; Rajeshwar, K. Handbook of Conducting Polymer s; 3rd ed.; Skotheim, T. A.; Elsenbaumer, R. L.; Reynolds, J. R., Eds.; Marcel Dekker: New York, 1998.

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16 either a 0.02 cm 2 platinum disk or indium-tin oxide coated glass slide working electrode, a coiled platinum wire as a counter electrode, and a silver wire pseudo-reference electrode. The pseudo-reference was calibrated vs the Fc/Fc + redox couple both before and after the experiments, and then converted to the SCE reference system. 3 Platinum-based interdigitated microelectrodes were supplied by Dr. Giovanni C. Fiaccabrino, Institute of Microtechnology (IMT), University of Neuchtel. The IME's consisted of a printed circuit board encapsulated in epoxy with the electrode area having 5 m m line widths, 5 m m gaps, 1 mm lengths, and 50 pairs of bands. A layer of silicon nitride on top of the platinum bands served as a passivation layer to limit polymer growth to the interdigitation region only. Electrochemical solvents must also be carefully chosen in order to avoid reaction of the solvent at the potentials applied (usually defined as background current densities less than 1 m A cm -2 ). Common solvents include water, acetonitrile, benzonitrile, tetrahydrofuran, propylene carbonate, and methylene chloride. 4 For the work described here, which exclusively used platinum and ITO as working electrodes, only acetonitrile, propylene carbonate, and methylene chloride offer the potential range required for both pand n-type doping. To achieve the maximum window, though, solvent purity and dryness are extremely important. 3. Noviandri, I.; Brown, K. N.; Fleming, D. S.; Gulyas, P. T.; Lay, P. A.; Masters, A. F.; Phillips, L. J. Phys. Chem. B 1999 , 103 , 6713-6722 4. (a) Adams, R. N. Electrochemistry at Solid Electrodes Marcel Dekker: New York, 1969. (b) Mann, C. K. Electroanal. Chem. 1969 , 3 , 57. (c) Sawyer, D. T.; Sobkowiak, A.; Roberts, J. L., Jr. Electrochemistry for Chemists, 2nd Ed. Wiley: New York, 1995. (d) Fry, J. Laboratory Techniques Electroanalytical Chemistry P. T. Kissenger and W. R. Heineman, Eds. Marcel Dekker: New York, 1996.

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17 2.2.2 Cyclic Voltammetry Cyclic voltammetry employs a saw-tooth waveform to vary potential linearly over time. Current is measured and a plot of current density as a function of potential is obtained. Conjugated polymers can be por n-type doped by either applying an oxidizing or reducing potential, respectively. When the polymer is in its insulating state, no current is passed between the working and counter electrodes. Upon doping, though, large amounts of current flow resulting in a peak. Cyclic voltammetry is a key technique for the study of conjugated polymers due to its ability to measure peak current (i p ), peak current density (j p ), and peak potential (E p ). 2.2.3 Differential Pulse Voltammetry Differential pulse voltammetry (DPV) offers several advantages when compared to cyclic voltammetry.This includes higher sensitivities than cyclic voltammetry leading to sharper current onsets near the formal potential region. 5 It is a faster experiment over the potential ranges being examined. The peak shapes seen in DPV also allude to the redox behavior of the systems. True reversible systems exhibit sharp, more well-defined bellshaped peaks, while quasi-reversible and irreversible systems give broader peaks with lower current densities than for reversible systems. In addition, the peak separation between the forward and reverse scans, D E, approaches 0 mV for reversible systems, but separates for quasi-reversible and irreversible systems. This technique also serves to minimize the background and capacitive currents; because it measures the differences between successive steps. To date, very little work has been done to examine the 5. Richardson, D. E.; Taube, H. Inorg. Chem. 1981 , 20 , 1278-1285.

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18 fundamental behavior of conjugated polymers using DPV, 6 rather efforts have been focused on sensor 7 and release applications. 8 2.2.4 In-situ Conductivity Traditionally, conductivity experiments have been performed using the four-point probe method on free-standing or substrate-supported films. Very little research, though, has been attempted on measuring conductivity in-situ as potential is varied to better understand redox property changes in conjugated polymers. In-situ conductance measurements were performed using a modification of the steady-state procedure described by the Wrighton group. 9 This procedure called for the working electrode of the bipotentiostat to serve as the gate and was "shorted" with the working electrode of the potentiostat/galvanostat and connected to one side of the interdigitated microelectrode (IME) bus. The other side of the IME bus was connected to the shorted reference and counter of potentiostat/galvanostat and served as the drain. The reference and counter electrodes of the bipotentiostat served as the corresponding working 6. (a) Jin, S.; Cong, S.; Zue, G.; Xiong, H.; Mansdorf, B.; Cheng, S. Z. D. Adv. Mater. 2002 , 14 , 1492-1496. (b) Nishiumi, T.; Higuchi, M.; Yamamoto, K. Electrochemistry 2002 , 70 , 668-670. 7. (a) Reynes, O.; Gulon, T.; Moutet, J.-C.; Royal, G.; Saint-Aman, E. J. Organomet. Chem. 2002 , 656 , 116-119. (b) Ekinci, E.; Erdogdu, G.; Karagozler, A. E. J. Appl. Poly. Sci. 2000 , 79 , 327-332. Ciszewski, A.; Milczarek, G. Anal. Chem. 1999 , 71 , 1055-1061. (c) Fabre, B.; Burlet, S.; Cespuglio, R.; Bidan, G. J. Electroanal. Chem. 1997 , 426 , 75-83. 8. (a) Diab, N.; Schuhmann, W. Electrochim. Acta 2001 , 13 , 860-867. (b) Komura, T.; Kijima, K.; Yamaguchi, T.; Takahashi, K. J. Electroanal. Chem. 2000 , 486 , 166-174. 9. (a) Schiavon, G.; Sitron, S.; Zotti, G. Synth. Met. 1989 , 32 , 209-217. (b) Kittlesen, G. P.; White, H. S.; Wrighton, M. S. J. Am. Chem. Soc. 1984 , 106 , 7389-7396. (c) Paul, E. W.; Ricco, A. J.; Wrighton, M. S. J. Phys. Chem. 1985 , 89 , 1441-1447. (d) Thackeray, J. W.; White, H. S.; Wrighton, M. S. J. Phys. Chem. 1985 , 89 , 5133-5140.

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19 and counter of the electrochemical cell. The electrical resistance of the polymer was determined at 50 mV intervals by holding the gate at the desired potential for one to two minutes to allow for equilibrium conditions and sweeping the drain potential from +20 mV to -20 mV at a sweep rate of 1 mV s -1 . The slope of the resulting line (E drain vs I drain ) was obtained using linear regression techniques (R 2 values greater than 0.98 for each case) and was taken to be the resistance of the film. 2.3 Optical Methods Two other critical methods for describing conjugated polymer behavior include spectroelectrochemistry and colorimetry. These techniques allow for an examination of changes in the energy of optical transitions upon doping, but also the energy of the band gap, along with the color and relative transmissivity of the polymer film as sensed by the human eye. 2.3.1 Spectroelectrochemistry Spectroelectrochemical experiments were performed using either a Varian Cary 5 spectrophotometer for benchtop work or a Stellernet Diode Array Vis-NIR spectrophotometer for dry box studies. Irrespective of the instrument used, all studies used a three electrode cell, as with the electrochemical studies, only with replacement of the working electrode with indium-tin oxide coated glass from Delta Technologies. Polymer films were deposited potentiostatically until 25 mC cm -2 (roughly 300 nm thickness) had passed in order to control the thickness of the polymer film. The films were then placed in monomer-free electrolyte solution and switched 20 times between the neutral and oxidized states to break-in the film. Then, the films were held at a reducing potential for 30 minutes to ensure that the films were completely de-doped. Spectra were collected by scanning the

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20 spectrophotometer and after each scan, the potentials was stepped in either 50 or 100 mV increments, and then rescanned. 2.3.2 Colorimetry Colorimetry provides a more precise way to define color than spectrophotometry. 10 Rather than measure absorption bands, colorimetry measures the human eye’s sensitivity to light across the visible region and gives a mathematical function to describe color. This technique measures three values in relation to color: the hue (dominant wavelength), which is the wavelength where maximum contrast occurs, saturation (purity), which is the color’s intensity, and brightness (luminance), which is the relative lightness of the color. The CIE 1931 system is used exclusively in these studies. For simplification, the horseshoe locus shown in Figure 2-1 is used to graphically represent the path of the polymer as it is doped. Wavelengths for the experiment are found on the locus itself and represent the “pure” color. Moving inwards towards the illuminant source leads to a lighter color as the purity decreases until white results at the illumination source. 10. (a) Kuehni, R. G. Color: an Introduction to Practice and Principles ; Wiley: New York, 1996. (b) Thompson, B. C.; Schottland, P.; Zong, K. W.; Reynolds, J. R. Chem. Mater. 2000 , 12 , 1563-1571.

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21 Figure 2-1. CIE 1931 coordinate

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22 CHAPTER 3 D-A MONOMER SYNTHESIS AND PROPERTIES 3.1 Introduction As mentioned in chapter 1, one of the greatest challenges to the field of conjugated polymers is the ability to generate an ambient stable n-type doped state along the polymer backbone. To date, there are no examples of n-type doped systems stable to ambient benchtop conditions due to the high reactivity of the anion charge carrier to oxygen and water. This chapter discusses the synthesis of a variety of monomers that seek to use “band gap engineering” to manipulate the corresponding polymer’s valence and conduction band levels to control optical and electrochemical properties. By controlling both the electron donating and electron accepting abilities of the monomer, it is expected that the corresponding polymers will have easily accessible oxidation and reduction potentials and lowered band gaps. In recent years, researchers have observed that introduction of nitrogen within the polymer repeat unit stabilizes the n-type doped state by lowering the LUMO such that reduction occurs more readily. As illustrated in Figure 3-1, the incorporation of a single nitrogen, pyridine for example, allows for reduction levels (2.15 V vs SCE) equivalent to biphenyl, which is a more extended aromatic system. Heterocycles containing multiple nitrogens have potentials even more positive than pyridine, and the relative placement of the nitrogens atoms is also an important factor. Incorporation of a second nitrogen shifts

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23 the reduction potential 300 mV more positive for pyrimidine and 500 mV more positive for pyrazine. Quinoxaline has a reduction potential of -1.09 V, while pyrido[3,4b ]pyrazine reduces at -0.85 V. This “nitrogen-effect” is due to the lower molecular orbital energy of nitrogen in comparison to carbon in these p -systems. 1 Of the systems shown in Figure 3-1, only the compounds highlighted in red have easily synthesizable dihalo derivatives, a requirement for metal-catalyzed coupling reactions used to make donor-acceptor monomers. A second important factor for lowering conduction band levels in nitrogencontaining heterocycles is the ability to be protonated. This effect is shown in the reduction potential of both pyridinium and pyrazinium being 1.4 V more positive than pyridine and pyrazine, respectively. Several groups have used this effect to reversibly lower the conduction band level, significantly shifting the electrochemical and optical properties of these systems. 2 This chapter details the synthesis and properties of the targeted donor-acceptor monomers shown in Figure 3-2. Two dialkoxythiophene derivatives have been chosen for 1. (a) Jenkins, I. H.; Rees, N. G.; Pickup, P. G. Chem. Mater. 1997 , 9 , 1213-1216. (b) Jenkins, I. H.; Salzner, U.; Pickup, P. G. Chem. Mater. 1996 , 8 , 2444-2450. (c) Kanbara, T.; Miyazaki, Y.; Yamamoto, T. J. Polym. Sci.. Part A: Polym. Chem. 1995 , 33 , 9991003. (d) Lee, B.-L.; Yamamoto, T. Macromolecules 1999 , 32 , 1375-1382. (e) Onada, M. J. Appl. Phys. 1995 , 78 , 1327-1333. (f) Saito, N.; Kanbara, T.; Kushida, T.; Kubota, K.; Yamamoto, T. Chem. Lett. 1993 , 1775-1778 . (g) Yamamoto, T. J. Polym. Sci., Part A: Polym. Chem. 1996 , 34 , 997-1001. (h) Yamamoto, T.; Zhou, Z.; Kanbara, T.; Shimura, M.; Kizu, K.; Maruyama, T.; Nakamura, Y.; Fukuda, T.; Lee, B.-L.; Ooba, N.; Tomaru, S.; Kurihara, T.; Kaino, T.; Kubota, K.; Sasaki, S. J. Am. Chem. Soc. 1996 , 118 , 10389-10399 . (i) Wiberg, K. B.; Lewis, T. P. J. Amer. Chem. Soc. 1970 , 92 , 7154-7160 2. (a) Martin, R. E.; Wytko, J. A.; Diederich, F.; Boudon, C.; Gisselbrecht, J.-P.; Gross, M. Helv. Chim. Acta 1999 , 82 , 1470-1485. (b) Wang, H.; Helgeson, R.; Ma, B.; Wudl, F. J. Org. Chem. 2000 , 65 , 5862-5867

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24 their high valence band levels and ease in their functionalization. 3 Both poly(3,4ethylenedioxythiophene) (PEDOT) and poly(3,3-dimethyl-3,4-dihydro-2 H -thieno[3,4b ][1,4]dioxepine) (ProDOT-Me 2 ) switch rapidly, have low oxidation potentials due to their Figure 3-1. Reduction potentials of common nitrogen containing heterocycles. Structures highlighted in red have either commercially available or easily synthesizable dihalo derivatives. Structures highlighted in blue have easily protonated sites. Adapted from ref. [2]. 3. (a) Jonas, F. Heywang, G.; Schidtberg, W. Novel polythiophenes, process for their preparation, and their use. German Patent DE 3,813,589, November 2, 1989. (b) Jonas, F. Heywang, G.; Schidtberg, W.; Heinze, J.; Dieterich, M. Polythiophenes, process for their preparation and their use. Eur. Patent App. EP 339,340, September 25, 1990. (c) Jonas, F. Heywang, G.; Schidtberg, W.; Heinze, J.; Dieterich, M. Polythiophenes, process for their preparation and their use. US Patent US 4,959,430, September 25, 1990. (d) Heywang, G.; Jonas, F. Adv. Mater. 1992 , 4 , 116-118. (e) Welsh, D. M.; Kumar, A.; Meijer, E. W.; Reynolds, J. R. Adv. Mater. 1999 , 11 , 1379-1382.

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25 low lying valence band levels, and are stable at a wide range of temperatures. Poly(ProDOT-Me 2 ) also has the highest change in transmittance upon doping of any of the poly(alkylenedioxythiophene)s. 4 To probe how electron acceptor strength affects the conduction band energy levels, pyridine, pyrazine, and pyrido[3,4b ]pyrazine were attempted to be incorporated within the donor structures to yield hybrid systems with compressed band gaps. This allows both oxidation and reduction to be readily accessible within the desired electrochemical window. The relative transmissivity of polymers synthesized from these systems is expected, and hoped, to increase by changing from EDOT to ProDOT-Me 2 in the visible region. Incorporation of trimethylsilyl groups at the polymerization sites has been shown to greatly enhance monomer solubility in acetonitrile and the quality of films prepared by electropolymerization. 5 3.2 Targeted Monomer Synthesis Two palladium catalyzed aryl-aryl cross-coupling routes were used to prepare the donor-acceptor monomer systems. Negishi 6 and Stille couplings 7 demonstrate yields in excess of 90% in combination with short reaction times (Figure 3-3). Each synthetic route offers distinct advantages. The Negishi coupling provides easy, in-situ preparation of the organic-zincate complex while also avoiding highly toxic tin reagents. However, the Stille 4. Kumar, A.; Welsh, D. M.; Morvant, M. C.; Piroux, F.; Abboud, K. A.; Reynolds, J. R. Chem. Mater. 1998 , 10 , 10, 896-902. 5. Sotzing, G. A.; Reynolds, J. R.; Steel, P. J. Adv. Mater. 1997 , 9 , 795-798 6. Negishi, E.; King, A. O.; Okukado, N. J. Org. Chem. 1977 , 42 , 1821-1823 7. Milstein, D.; Stille, J. K. J. Amer. Chem. Soc. 1979 , 10 1, 4992-4998

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26 Figure 3-2. Donor-acceptor-donor XDOT-pyridine monomers targeted for synthesis. Terminal 3,4-alkylenedioxythiophenes allow for easily accessible oxidation potentials for electrochemical polymerization.

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27 coupling provides an easily isolable stannyl intermediate allowing effective monomer purification. This stannyl intermediate can be synthesized in both high yields and large quantities for future monomer syntheses. The Stille reaction also uses a less expensive, less oxygen reactive catalyst in trans -dichlorobis -triphenylphosphinepalladium (II) for coupling with dibromides. Alternatively, bis -(trit -butylphosphine)palladium (0) can be used. 8 In fact, the Pd(0) complex permits the Stille coupling of aromatic dichlorides, which are often easier to prepare than other dihalo aromatics. Typical Negishi couplings use tetrakis -triphenylphosphine palladium(0), a highly oxyphilic catalyst that has issues of questionable quality when ordered through commercial vendors. In its pure state, this catalyst is a bright, canary yellow solid, but may decompose to the green oxidized palladium (II) state during shipping. Removal of the palladium (II) impurity requires recrystallization using Schlenk techniques and is highly labor intensive. 3.2.1 Donor Syntheses In order to prepare the Stille reagent, distillation of EDOT from calcium hydride to give a clear, colorless oil is preferred to enhance yields upon lithiation. Both trimethylsilyl and non-trimethylsilyl substituted tin EDOT‘s can be prepared in high yield by lithiation with n -butyl lithium and subsequent quenching with trimethyltin chloride as shown in Figure 3-4. (2,3-Dihydro-thieno[3,4b ][1,4]dioxin-5-yl)-trimethyl-stannane ( 2 ) was prepared in 95% yield 9 and trimethyl-(7-trimethylstannanyl-2,3-dihydro-thieno[3,48. Littke, A. F.; Schwarz, L.; Fu, G. C. J. Amer. Chem. Soc. 2002 , 124 , 6343-6348. 9. (a) Cao, J.; Kampf, J. W.; Curtis, M. D. Chem. Mater. 2003 , 15 , 404-411. (b) DuBois, C. J.; Reynolds, J. R. Adv. Mater. 2002 , 14 , 1844-1846. (c) Wang, F.; Wilson, M. S.; Rauh, R. D.; Schottland, P.; Thompson, B. C.; Reynolds, J. R. Macromolecules 2000 , 33 , 2083-2091.

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28 b ][1,4]dioxin-5-yl)-silane ( 4 ) in 88% yield. Both compounds are white waxy solids with a pungent odor. Purification was performed by initially melting the solids and then distillation under vacuum with a warmed apparatus. The key to successful distillation is preventing the compounds solidification in the condenser. In this case no water was used to cool the apparatus, and a heat gun was used occasionally to prevent blockage. Since organotins are highly toxic, the compounds were kept frozen to lower their vapor pressure and prevent decomposition. Figure 3-3. Negishi and Stille coupling routes to BEDOT-pyridines. a.) i. n -BuLi, THF, 78 C, 1 hr. ii. ZnCl 2 , 0 C, 1 hr. b.) 2,5-dibromopyridine, Pd(PPh 3 ) 4 , 65 C, 3 hr. c.) i. n BuLi, THF, -78 C, 1 hr. ii. (H 3 C) 3 SnCl, room temperature, 3 hr. d.) 5,8-dibromo-2,3diphenyl-pyrido[3,4b ]pyrazine, PdCl 2 (PPh 3 ) 2 , DMF, 90 C, 6 hr. Figure 3-4. Preparation of Stille reagents for aryl-aryl cross-coupling reactions using palladium catalysts. a.) i. n -BuLi, THF, -78 C, 90 min. ii. (H 3 C) 3 SnCl, 25 C, overnight. b.) i. n -BuLi, THF, -78 C, 90 min. ii. (H 3 C) 3 SiCl, 0 C, 1 hr. iii. n -BuLi, THF, -78 C, 90 min. iv. (H 3 C) 3 SnCl, 25 C, overnight.

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29 As outlined in Figure 3-5, preparation of ProDOT-Me 2 [2] e ( 8 ) as a donor species for the highly substituted monomers begins with exhaustive bromination of thiophene to prepare 2,3,4,5-tetrabromothiophene ( 5 ). 10 This reaction can be performed on the kilogram scale in high yield. Maximizing yield in these steps is critical as the molecular weight drops by roughly 60% from 2,3,4,5-tetrabromothiophene to 3,4dimethoxythiophene ( 6 ). Purification is performed by simply washing the final product with cold acetone to give white needles. Preparation of 6 10c,d,g, 11 has traditionally been performed by zinc reduction in refluxing acetic acid, 11c Grignard formation with elemental magnesium, 10b by using sodium or potassium amides in liquid ammonia, 12 or by using palladium-catalyzed hydrodebromination. 11i,j However, these three reactions require expensive reagents and time consuming or mult-step syntheses. A more facile route was developed using n butyllithium. A lithium-halogen exchange in the substrate is followed by quenching with 10. (a) Blockhuys, F.; Rousseau, B.; Peeters, L. D.; Van Alsenoy, C.; Geise, H. J.; Kataeva, O. N.; Van der Veken, B.; Herrebout, W. A. J. Phys. Chem. A 2000 , 104 , 8983-8988. (b) Gronowitz, S.; Moses, P.; Hakansson, R. Ark. Kemi 1960 , 16 , 267. (c) Langeveld-Voss, B. M. W.; Janssen, R. A. J.; Meijer, E. W. J. Molec. Struct. 2000 , 521 , 285-301. (d) Lawesson, S. Acta Chem. Scand . 1956 , 10 , 1020. (e) Tour, J. M.; Wu, R. Macromolecules 1992 , 25 , 1901-1907. 11. (a) D'Auria, M.; De Mico, A.; D'Onofrio, F.; Piancatelli, G. J. Chem. Society, Perkin Trans. 1 1987 , 1777-1780. (b) Dapperheld, S.; Feldhues, M.; Litterer, H.; Sistig, F.; Wegener, P. Synthesis 1990 , 403-405. (c) Gronowitz, S. Acta Chem. Scand. 1959 , 13 , 1045. (d) Gronowitz, S.; Moses, P. Acta Chem. Scand. 1962 , 16 , 105-110. (e) Inaoka, S.; Collard, D. M. J. Mater. Chem. 1999 , 9 , 1719-1725. (f) Moses, P.; Gronowitz, S. Ark. Kemi 1961 , 18 , 119. (g) Xie, Y.; Ng, S.C.; Wu, B.-M.; Xue, F.; Mak, T. C. W.; Hor, T. S. A. J. Organomet. Chem. 1997 , 531 , 175-181. (h) Xie, Y.; Wu, B.-M.; Xue, F.; Ng, S.-C.; Mak, T. C. W.; Hor, T. S. A. Organometallics 1998 , 17 , 3988-3995. (i) Ye, X.-S.; Wong, H. N. C. J. Org. Chem. 1997 , 62 , 1940-1954. 12. Reinecke, M. G.; Adickes, H. W.; Pyun, C. J. Org. Chem. 1971 , 36 , 2690-2692.

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30 water to give 83% of the desired compound after purification by distillation. This debromination reaction was performed on up to 500 g quantities of 5 in only several hours. Conversion of 6 to 7 occurs via an Ullman ether coupling using sodium methoxide in methanol and copper(II) oxide. [10]c, 13 This reaction step incurs the most material cost due to a low yield of 64%. Commercial preparation of EDOT involves Williamson etherification with a thiophene-based diester diol and 1,2-dichloroethane. [3]d,[4] Due to the bulky neopentyl glycol used for ring closure to form the dioxepine ring, 8 is better synthesized by a transetherification route using a catalytic amount of p -toluenesulfonic acid and azeotropic distillation to drive the equilibrium by removal of methanol. [4]e, 14 Conversion of 7 to 8 also proceeds at a slightly lower yield of 61%. The overall yield is 24% with the majority of material lost in the final two steps. The versatility of this route lies in the ability of many different 2,2-substituted-1,3-diols to be used. Thus, the ProDOT family can be expanded to monomers, which provide highly soluble polymers systems by the introduction of aliphatic side groups. 15 An alternative method of preparing 6 was also explored on the hypothesis that trimethylsilane could be used as a protecting group for the thiophene a -positions prior to 13. (e) Goldoni, F.; Langeveld-Voss, B. M. W.; Meijer, E. W. Synth. Commun. 1998 , 28 , 2237-2244. (a) Gronowitz, S. Ark. Kemi 1958 , 12 , 239. (b) Henrio, G.; Morel, J.; Pastour, P. Tetrahedron 1977 , 33 , 191-198. (c) Keegstra, M. A.; Peters, T. H. A.; Brandsma, L. Tetrahedron 1992 , 48 , 3633-3652. (d) Merz, A.; Rehm, C. J. Prakt. Chem. / Chem.-Ztg 1996 , 338 , 672-674. 14. Pratt, E. F.; Draper, J. D. J. Amer. Chem. Soc. 1949 , 71 , 2846-2849. 15. Welsh, D. M.; Kloeppner, L. J.; Madrigal, L.; Pinto, M. R.; Thompson, B. C.; Schanze, K. S.; Abboud, K. A.; Powell, D.; Reynolds, J. R. Macromolecules 2002 , 35 , 6517-6525.

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31 bromination (Figure 3-6). However, lithiation of the bis-TMS-thiophene ( 9 ) 16 led to rearranged products, possibly via a mechanism similar to the halogen dance known for thiophenes. 11, 17 Figure 3-5. Preparation of ProDOT-Me 2 . a.) Br 2 , CHCl 3 , 25 C, 24 hr. b.) i. n -BuLi, THF, 0 C. ii. ice. c.) NaOMe, MeOH, CuO, KI, D, 3 days . d.) neopentyl glycol, p -TSA, toluene, 4 sieves, D, 24 hr . 16. (a) Barton, T. J.; Hussmann, G. P. J. Org. Chem. 1985 , 50 , 5881-5882. (b) Block, E.; Birringer, M.; DeOrazio, R.; Fabian, J.; Glass, R. S.; Guo, C.; He, C.; Lorance, E.; Qian, Q.; Schroeder, T. B.; Shan, Z.; Thiruvazhi, M.; Wilson, G. S.; Zhang, Z. J. Am. Chem. Soc. 2000 , 122 , 5052-5064. (c) Bock, H.; Roth, B. Phosphorus Sulfur Relat. Elem. 1983 , 14 , 211-224. (d) Deffieux, D.; Bonafoux, D.; Bordeau, M.; Biran, C.; Dunogus, J. Organometallics 1996 , 15 , 2041-2046. (e) Furukawa, N.; Hoshiai, H.; Shibutani, T.; Higaki, M.; Iwasaki, F.; Fujihara, H. Heterocycles 1992 , 34 , 1085-1088. (f) Lukevics, E.; Arsenyan, P.; Belyakov, S.; Popelis, J.; Olga, P. Tetrahedron Lett. 2001 , 42 , 2039. (g) O’Donovan, A. R. M.; Shepherd, M. K. Tetrahedron Lett. 1994 , 35 , 4425-4428. (h) Pratt, J. R.; Pinkerton, F. H.; Thames, S. F. J . Orgonomet. Chem. 1972 , 38 , 24. (i) Ritter, S. K.; Noftle, R. E. Chem. Mater. 1992 , 4 , 872-879. (j) van Pham, C.; Macomber, R. S.; Mark, H. B., Jr. J. Org. Chem. 1984 , 49 , 5250-5253. Figure 3-6. Preparation of 3,4-dibromothiophene from bis-TMS thiophene. a.) i. n -BuLi, 78 C, THF, 1 hr,. ii. (H 3 C) 3 SiCl, -78 C to 25 C. iii, n -BuLi, -78 C, THF, 1 hr. iv. (H 3 C) 3 SiCl, -78 C to 25 C. b.) i. LDA, -78 C, 1 hr. ii. 1,2-dibromoethane, -78 C to 25 C. c.) 2 eq KF or TBAF 17. (a) Bremner, D. H.; Mitchell, S. R. Ultrasonics Sonochemistry 1999 , 6 , 171-173. (b) Froehlich, H.; Kalt, W. J. Org. Chem. 1990 , 55 , 2993-2995. (c) Kano, S.; Yuasa, Y.; Yokomatsu, T.; Shibuya, S. Heterocycles 1983 , 20 , 2035-2037. (d) Mubarak, M. S.; Peters, D. G. J. Org. Chem. 1996 , 61 , 8074-8078.

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32 3.2.2 Acceptor Syntheses Substituted pyrido[3,4-b]pyrazines can be prepared in two steps as shown in Figure 3-7. Bromination of commercially available 3,4-diaminopyridine in 48% hydrobromic acid demonstrates yields ranging from 25 to 95%. 1d No explanation is known for the range of yields for this reaction as they were independent of both scale and reaction time. Ring closure with an appropriate diketone forms the aromatic diimine in 87% yield for the unsubstituted pyrido[3,4b ]pyrazine ( 12 ), but 38% for the phenyl-substituted derivative ( 13 ). 1d The lower yields for the phenyl derivative are possibly due to the deactivation of the amine groups to nucleophilic attack by the presence of the bromide groups. The non-brominated 2,3-diphenyl-pyrido[3,4b ]pyrazine homoacceptor ( 10 ) can be prepared in 87% yield 18 and provides information on the energy levels and reduction potentials for the pyrido[3,4b ]pyrazine systems. 18. a) Armand, . Can. J. Chem. 1978 , 56 , 1804-1814. (b) Clark-Lewis, .; Singh, . J. Chem. Soc. 1962 , 3162-3164. (c) Duarte, F. F.; Popp, F. D. J. Heterocycl. Chem. 1994 , 31 , 819-824. Figure 3-7. Preparation of pyrido[3,4b ]pyrazines from 3,4-diaminopyridine. a.) benzil, n butanol, D . b.) Br 2 , HBr, D . c.) glyoxal, n -butanol, D . d.) benzil, n -butanol, D .

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33 Only three methods of preparing 2,5-dibromopyrazines exist in the literature. Traditional methods of electrophilic aromatic substitution do not work with pyrazine due to ring decomposition leading to unisolatable and uncharacterizable compounds. 19 The only method of direct bromination requires a gas-phase reaction at high temperatures which also leads to mostly decomposition products. 20 Other methods have been developed to overcome this problem with the first method, summarized in Figure 3-8, involving preparation of 2,5-dibromopyrazine ( 18 ) via pyrazinoic acid. The second method, as shown in Figure 3-9, details attempted preparation of 18 from 2-aminopyrazine. The third method, not detailed here, uses hydrazine as a reducing agent that reacts with 2,3,5,6tetrabromopyrazine to form a hydrazopyrazine intermediate that can be subsequently decomposed to form 18 . The first step of the method attempted in Figure 3-8 begins with the formation of 3amino-pyrazine-2-carboxylic acid methyl ester ( 14 ) by the addition of acidic methanol to 3-aminopyrazinoic acid. 21 The reaction proceeded in 40% yield; much lower than the expected 72% yield. The lowered yield is thought to be due to the high water solubility of the product, so a more aliphatic derivative, 3-amino-pyrazine-2-carboxylic acid butyl ester ( 19 ), was attempted. Similar experimental conditions were employed using n -butanol, 19. Stoehr J. Prakt. Chem. 1895 , 51 , 456. 20. Hertog, H. J. den; Wibaut, J. P. Rec. Trav. Chim. 1932 , 51 , 381. 21. (a) Chen, J. J.; Hinkley, J. M.; Wise, D. S.; Townsend, L. B. Synth. Commun. 1996 , 26 , 617-622. (b) Ellingson, R. C.; Henry, R. L.; McDonald, F. G. J. Am. Chem. Soc. 1945 , 67 , 1711-1713. (c) Hurd, C. D.; Bethune, V. G. J. Org. Chem . 1970 , 35 , 14711475. (d) Katoh, A.; Ohkanda, J.; Sato, H.; Sakamoto, T.; Mitsuhashi, K. Heterocycles 1993 , 35 , 949-954. (e) Shutske, G. M.; Agnew, M. N. J. Heterocycl. Chem. 1981 , 18 , 1025.

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34 nevertheless, no butyl ester product was recovered, most likely due to dehydration of butanol to form 1-butene. Milligram quantities of 19 could be prepared by refluxing 3aminopyrazinoic acid with a one equivalent of p -toluenesulfonic acid in excess n -butanol. However, upon scale up only starting materials were isolated. The next step involved preparation of 3-amino-6-bromo-pyrazine-2-carboxylic acid ( 15 ) via bromination and subsequent saponification. 22 14 was dissolved in warm acetic acid, and bromine was added dropwise to form 3-amino-6-bromo-pyrazine-2carboxylic acid methyl ester ( 15 ) in situ . After saponification, acidification afforded a precipitate that was filtered to give a 21% yield upon recrystallization. NOTE: The product violently decomposed at 188 C, when a melting point was attempted destroying the melting point capillary. The yield here is lower than the 90% expected, possible due to the product’s high water solubility and sparing solubility in organic solvents. Attempts were made to extract the aqueous solution with methylene chloride, chloroform, benzene, and toluene; however, no product was isolated from the organic solvent upon evaporation. Decarboxylation was performed in refluxing decalin to give 5-bromo-pyrazin-2-ylamine ( 17a ) in 40% yield rather than the quantitative yield reported previously. 22 The remainder of the material isolated was starting material. At this point, the overall yield for this series of reactions was 3%. A successful, high-yielding method for preparing 5-bromo-pyrazin-2-ylamine ( 17b ) is the bromination of 2-aminopyrazine with N -bromosuccinimide which resulted in 33% yield as shown in Figure 3-9. In fact, this route allowed for the use of less expensive starting materials and overall higher yielding reactions in fewer steps. 23 22. Ellingson, R. C.; Henry, R. L. J. Amer. Chem. Soc. 1949 , 71 , 2798-2800.

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35 Several methods were investigated to transform the 17a-b into the corresponding 2,5-dibromopyrazine. Repeated attempts at diazotization failed to produce the desired 2,5dibromide ( 18 ) following literature procedures. Several Sandmeyer reactions were also attempted using copper (I) bromide to form 18 and potassium iodide to form the corresponding 2-bromo-5-iodo-pyrazine compound. Once again all attempts to produce 18 23. (a) de Bie, D. A.; Ostrowicz, A.; Geurtsen, G.; Van der Plas, H. C. Tetrahedron 1988 , 44 , 2977-2983. (b) Sato, N. J. Heterocycl. Chem. 1982 , 19 , 673-674. (c) Stanovnik, B.; Tisler, M.; Drnovsek, I. Synthesis 1981 , 12 , 987-989. Figure 3-8. Attempted preparation of 2,5-dibromopyrazine from 3-aminopyrazinoic acid. a.) MeOH, H 2 SO 4 . b.) i. AcOH, Br 2 . c.) i. NaOH, H 2 O, ii. HBr. d.) decalin, D . e) i. Br 2 , -5 C. ii. NaNO 2 , dropwise. iii. NaOH/H 2 O to pH 7.1. Figure 3-9. Preparation of 5-bromo-pyrazin-2-ylamine with NBS from aminopyrazine. a.) NBS, CHCl 3 , 0 C.

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36 resulted in no obtainable yields. After an exhaustive literature search, it was found that pyrazines do not readily undergo diazotization or Sandmeyer-type reactions using traditional techniques. Only by use of nitrosylsulfuric acid in concentrated sulfuric acid were researchers able to obtain the desired product. 24 In each attempt, the reaction mixture was seen to release nitrogen at 0 C. Cooling the reaction below this temperature only resulted in the recovery of starting material. The failure of the reaction is most likely due to the rate of hydrolysis being much faster than the rate of halogen addition to the intermediate diazo compound. 25 Another method for preparing dihalo derivatives of pyrazine uses fluorine as an ortho -directing group as shown in Figure 3-10. 26 The reaction begins with the conversion of chloropyrazine to fluoropyrazine ( 19 ) using potassium fluoride and 18-crown-6 in refluxing 1-methyl-2-pyrrolidone, but no product was observed after repeated attempts. If this step had succeeded, the last step would have involved lithiation using lithium 2,2,6,6tetramethylpiperidide, followed by quenching with iodine to form 3-fluoro-2,5-diiodopyrazine ( 20 ). 24. Gabriel, S.; Sonn, A. Ber. 1907 , 40 , 4851. 25. Erickson, A. E.; Speirri, P. E. J. Amer. Chem. Soc. 1946 , 68 , 400-402 26. (a) Pl, N.; Turck, A.; Heynderickx, A. Quguiner, G. Tetrahedron 1998 , 54 , 48994912. (b) Toudic, F.; Pl, N.; Turck, A.; Quguiner, G. Tetrahedron 2002 , 58 , 283-293 Figure 3-10. Preparation of 3-fluoro-2,5-diiodopyrazine from chloropyrazine. a.) KF, 18crown-6, NMP, D . b.) LDA, I 2 .

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37 The last method attempted in the preparation of dihalopyrazines involved the synthesis of 2,5-dichloropyrazine ( 22 ) using an N -oxide as a directing group for chlorination. 27 3-Chloropyrazine-1-oxide ( 21 ) was prepared by refluxing 2chloropyrazine, 40% hydrogen peroxide, and glacial acetic acid for three days (Figure 311). Recrystallization in ethanol gave 21 in 57% yield. 28 It has been shown that N oxidation always occurs on the nitrogen farthest from the halogen or electron-donating substituent, so no 2-chloropyrazine-1-oxide was isolated. 29 Chlorination of 21 with phosphorus oxychloride [28]a, 30 gave two products by TLC, neither being starting material. Distillation was attempted, but only column chromatography was able to purify the sample to give a clear liquid that melted at approximately 0 C. TLC showed only one spot, but NMR confirmed a 1:1 mixture of what was thought to be 21 and 2,6-dichloropyrazine. After further examination of the literature, it was found that chlorination using the above method does not lead to a mixture of 21 and 2,6-dichloropyrazine, but rather a mixture of the 2,3and 2,6-substituted pyrazines. 31 27. (a) Klein, B.; Berkowitz, J. J. Amer. Chem. Soc. 1959 , 81 , 5160-5166.(b) Klein, B.; Hetman, N. E.; O' Donnell, M. E. J. Org. Chem. 1963 , 28 , 1682-1686. (c) Palamidessi, G.; Bernardi, L. J. Org. Chem. 1964 , 29 , 2491-2492. (d) Sato, N.; Fujii, M. J. Heterocycl. Chem. 1994 , 31 , 1177-1180. 28. (a) Hashimoto, M.; Izuchi, N.; Sakata, K. J. Heterocycl. Chem. 1988 , 25 , 1705-1708. (b) Klein, B.; Hetman, N. E.; O’Donnell, M. E. J. Org. Chem. 1963 , 28 , 1682-1686. (c) Mixan, C. E.; Pew, R. G. J. Org. Chem. 1977 , 42 , 1869-1871. (d) Okada, S.; Kosasayama, A.; Konno, T.; Uchimaru, F. Chem. Pharm. Bull. 1971 , 19 , 1344-1357. (e) Sato, N. J. Org. Chem. 1978 , 43 , 3367-3370. 29. Baxter, R. A.; Newbold, G. T.; Spring, F. S. J. Chem. Soc. 1948 , 1859-1862 30. Eisch, J.; Gilman, H. Chem. Rev . 1957 , 57 , 525-581 31. Palamidessi, G.; Bernardi, L. J. Org. Chem. 1964 , 29 , 2491-2492

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38 3.2.3 Donor-Acceptor-Donor Monomer Syntheses Synthesis of the described donor-acceptor-donor monomers used palladium catalyzed aryl-aryl coupling as shown in Figure 3-13. All EDOT derivatives were synthesized using the Stille method due to the ability to prepare the EDOT-tin reagent in multi-gram quantities. BEDOT-Pyr ( 1 )was synthesized in 91% yield as a bright yellow solid. 32 Both BEDOT-PyrPyr ( 25 ) and BEDOT-PyrPyr-Ph 2 ( 3 )are bright red solids with low solubilities in all solvents when compared to 1 . Attempts at purification of 25 using silica column chromatography or recrystallization led to the opening of the diimine ring and subsequent decomposition. 3 was prepared in 98% yield during the final coupling step. 32a In order to enhance the solubility of the monomer systems, TMS substituted derivatives were synthesized (Figure 3-14). Problems with purification were encountered due to the fact that TMS-thiophenes cleave on purification with silica-based column chromatography due to its residual acidity. Purification with alumina-based column chromatography was tried, but impurities remained. Purification was also attempted using alumina, reverse phase HPLC, and recrystallization; however, impurities were unable to be removed. Figure 3-11. Attempted preparation of 2,5-dichloropyrazine from chloropyrazine. a.) H 2 O 2 , AcOH, D . b.) POCl 3 32. (a) DuBois, C. J.; Reynolds, J. R. Adv. Mater. 2002 , 14 , 1844-1846. (b) Irvin, D. J. Modifications of Electronic Properties of Conjugated Polymers. Ph. D. Dissertation, University of Florida, Gainesville, FL, 1998.

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39 ProDOT-Me 2 substituted systems were all synthesized by Negishi coupling reactions as outlined in Figure 3-15. BProDOT-Me 2 -Pyr ( 29 ) was synthesized in 50% yield as a bright yellow solid and purified by column chromatography. BProDOT-Me 2 PyrPyr-Ph 2 ( 30 ) was also synthesized in 50% yield as a bright orange solid and purified using column chromatography. The decreased yield is thought to result from imperfect formation of the reactive zincate by deprotonation using n -BuLi. Figure 3-12. Preparation of BEDOT-Pyridines. a.) 2,5-dibromopyridine, PdCl 2 (PPh 3 ) 2 . b.) 5,8-dibromo-pyrido[3,4b ]pyrazine, PdCl 2 (PPh 3 ) 2 . c.) 5,8-dibromo-2,3-diphenylpyrido[3,4b ]pyrazine, PdCl 2 (PPh 3 ) 2 Figure 3-13. Preparation of TMS-BEDOT-Pyridines. a.) 5,8-dibromo-2,3-diphenylpyrido[3,4b ]pyrazine, PdCl 2 (PPh 3 ) 2 . b.) 2,5-dibromopyridine, PdCl 2 (PPh 3 ) 2 . c.) 5,8dibromo-pyrido[3,4b ]pyrazine, PdCl 2 (PPh 3 ) 2

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40 3.3 Monomer Structure and Properties 3.3.1 NMR Examination of 1 H NMR chemical shifts in the aromatic region, specifically, focusing on the proton adjacent to the pyridine N in the acceptor, yields interesting results. All of the molecules detailed in this chapter contain a single C-H bond on carbon-5 of the pyridine ring. Deshielding effects can be examined with the proton’s chemical shift; a chemical shift that is further downfield relative to TMS is more affected by ring current, so systems with a high p -character density are expected to have further downfield shifts than those with less density. In Figure 3-15, the systems discussed in this chapter are ranked from the most shielding, or upfield shift, of the resonance of carbon-6 to the least. 3 has the most deshielded site with the C6-H resonance at 9.76 ppm. 30 only slightly more shielded with its C6-H resonance at 9.56 ppm. The thiophene-containing pyrido[3,4b ]pyrazine, 2,3-diphenyl-5,8-di-thiophen-2-yl-pyrido[3,4b ]pyrazine, has this proton resonance at 9.37 ppm, illustrating that thiophene is a less effective electron-donor than EDOT. 1c By decreasing the acceptor strength from PyrPyr to pyridine, the chemical shift moves upfield by 1 ppm for both 1 and 29 to 8.90 ppm. Bis-thienylpyridine, 2,5-dithiophen-2-yl-pyridine, has this resonance at 8.74 ppm further illustrating the point that Figure 3-14. Preparation of BProDOT-Me 2 -Pyridines. a.) i. n -BuLi, -78 C. ii. ZnCl 2 , 0 C. iii. Pd(PPh 3 ) 4 , 2,5-dibromopyridine. b.) i. n -BuLi, -78 C. ii. ZnCl 2 , 0 C. iii. Pd(PPh 3 ) 4 , 5,8-dibromo-2,3-diphenyl-pyrido[3,4b ]pyrazine.

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41 thiophene is a poorer electron-donor than EDOT. Systems with no donor attached display the most shielded carbon-6 sites with Br 2 -PyrPyr-Hex 2 having the most shielded site of all the pyridines. Figure 3-15. NMR aromatic chemical shifts of substituted pyridines. The compounds are ranked top to bottom from strongest to weakest D-A effect. Each experiment was performed in CDCl 3 (residual proton peak at 7.26 ppm).

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42 3.3.2 X-ray crystallography Several different methods were attempted in the growth of single crystals of the DA-D monomers that included solvent evaporation in NMR tubes and solvent-non-solvent diffusion. Unfortunately, only compound 3 gave x-ray quality crystals. The remaining compounds simply powdered out of solution. Data for 3 were collected at 173 K on a Siemens SMART PLATFORM equipped with a CCD area detector and a graphite monochromator utilizing MoK a radiation ( l = 0.71073 ). Cell parameters were refined using up to 8192 reflections. A full sphere of data (1850 frames) was collected using the w -scan method (0.3 frame width). The first 50 frames were remeasured at the end of data collection to monitor instrument and crystal stability (maximum correction on I was < 1%). Absorption corrections by integration were applied based on measured indexed crystal faces. The structure was solved by the Direct Methods in SHELXTL5, and refined using full-matrix least squares. 33 The non-H atoms were treated anisotropically, whereas the hydrogen atoms were calculated in ideal positions and were riding on their respective carbon atoms. The space group, P212121, is chiral, thus only one enantiomer exists in the crystal. The correct enantiomer is reported here judging by the value of a Flack parameter of -0.02(11). A total of 361 parameters were refined in the final cycle of refinement using 13405 reflections with I > 2 s (I) to yield R 1 and wR 2 of 5.32% and 11.92%, respectively. Refinement was done using F 2 . 33. Sheldrick, G. M. SHELXTL6 . Bruker-AXS, Madison, Wisconsin, USA, 2000 .

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43 3.3.3 UV-Vis The UV-Vis spectra of the pyridine-based monomers in methylene chloride are shown in Figure 3-18 along with EDOT, ProDOT-Me 2 , and pyridine for comparison. EDOT has a l max of 259 nm and a molar absorptivity of 15,700 L mol -1 cm -1 . Introduction of a dioxepine ring to make ProDOT-Me 2 yields a l max of 253 nm and lower molar absorptivity of 8,280 L mol -1 cm -1 . In more highly conjugated monomers the magnitude of l max and molar absorptivities is reversed with 29 having an e value of 58,400 L mol -1 cm -1 and l max of 357 nm. The trend can also be observed with 1 having a molar absorptivity of 36,400 L mol -1 cm -1 and of 351 nm. Both monomers are light yellow solids. Figure 3-16. Top and edge view of the crystal structure of BEDOT-PyrPyr-Ph 2 . The phenyl rings have been removed in the edge view to enhance visibility of the monomer backbone.

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44 In comparison to the thiophene-containing systems, 2,5-di-thiophen-2-yl-pyridine has a l max at 340 nm. 34 Introduction of the stronger pyrido[3,4b ]pyrazine acceptor leads to dramatic red shifts of the monomer absorptions when compared to the pyridine monomers as shown in Figure 3-19. 3 is a bright red solid that has four major UV-Vis absorptions with their corresponding l max ( e ) values of 228 (352,000 L mol -1 cm -1 ), 272 (190,000 L mol -1 cm -1 ), 325 (340,000 L mol -1 cm -1 ), and 478 nm (100,000 L mol -1 cm -1 ). Exchanging the EDOT Figure 3-17. UV-Vis of BXDOT-pyridines and their corresponding donor and acceptor components in methylene chloride. 34. Sease, J. W.; Zechmeister, L. J. Amer. Chem. Soc. 1947 , 69 , 270-273

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45 with ProDOT-Me 2 to give 30 yields a bright orange solid with a blue shifted absorption. Values for l max are 228 (352,000 L mol -1 cm -1 ), 264 (220,000 L mol -1 cm -1 ), 312 (290,000 L mol -1 cm -1 ), and 445 nm (91,000 L mol -1 cm -1 ). Substitution of the alkylenedioxythiophenes with thiophene to form 2,3-diphenyl-5,8-di-thiophen-2-ylpyrido[3,4b ]pyrazine leads to a l max value of 449 nm, virtually identical with that of 30 . This suggests that 30 is not as strong a donor-acceptor compound as BEDOT-PyrPyr-Ph 2 . Even though the donor-acceptor monomers detailed here are more highly conjugated than their corresponding donor or acceptor components, these systems are greater than the sum of their parts. The dramatic red shifts in absorption maxima of the monomers suggest that there is a high order of charge-transfer when compared to similar systems that do not have as strong electron donating or accepting sub-units. These red shifts are expected to be even more substantial upon polymerization. 35 3.3.4 Colorimetry Colorimetry performed on the UV-Vis solutions is illustrated in Figure 3-19. The pyridine-based monomers have only a slight tailing into the high energy portion of the visible region and appear almost colorless. Both 1 and 29 have x-y values near the illumination source. 1 has a relative luminance value of 99% and an x-y value of 0.360, 0.389. Due to the slightly broader absorption of 29 , its solution appears more yellow. This monomer has a relative luminance value of 98% and an x-y value of 0.374, 0.411. Both 3 and 30 are intensely colored with x-y values that lie very close to the horseshoe locus indicating a high color purity. 3 has a relative luminance of 71% and an x-y value of 0.490, 35. Briegleb, G. Elekronen-Donator Acceptor-Komplexes ; Springer: Berlin, 1961.

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46 0.477. 30 has a relative luminance of 49% and an x-y value of 0.544, 0.431. The color of the solutions are also shown in the upper right hand corner of Figure 3-20. 3.3.5 Electrochemistry Solution electrochemistry of the PyrPyr-Ph 2 acceptor unit along with the 3 and 30 is shown in Figure 3-21. The PyrPyr-Ph 2 acceptor-only electrochemistry has an E 1/2 value of -0.96 V vs SCE. Incorporation of an electron rich bi-EDOT donor into the structure gives a small negative shift in the E 1/2 value to -1.02 V for 3 . As expected, no further change is seen in the E 1/2 value for 30 monomer. It has been shown previously that there is a direct correlation between reduction E 1/2 values and the lowest unoccupied molecular Figure 3-18. UV-Vis of BXDOT-pyrido[3,4b ]pyrazines and their corresponding donor and acceptor components in methylene chloride.

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47 orbital (LUMO), so monomer reduction potentials provide a way to compare LUMO levels with those of the more delocalized polymer systems. 36 Figure 3-19. Colorimetry of the BXDOT-pyridines in methylene chloride. 36. (a) Streitwieser, A., Jr. Molecular Orbital Theory for Organic Chemists ; Wiley: New York, NY, 1961. (b) Streitwieser, A.; Schwager, I. J. Phys. Chem. 1962 , 66 , 23162320.

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48 3.4 Summary Eight new donor-acceptor-donor monomers (compounds 1 , 3 , 25 30 ) were successfully prepared using palladium catalyzed aryl-aryl cross-coupling reactions. As shown in Fugre 3-2, the relative strength of the acceptor content increases from pyridine to pyrido[3,4b ]pyrazine and is expected to lead to more stabilized reduced states in the resulting polymers. The pyrazine-containing monomers, unfortunately, could not be prepared due to the inability to synthesize the dihalo derivatives. Figure 3-20. Solution cyclic voltammetry of BEDOT-PyrPyr-Ph 2 , BProDOT-Me 2 PyrPyr-Ph 2 , and PyrPyr-Ph 2 . All monomers were 5 mM in acetonitrile with 0.1 M TBAP as electrolyte. In order to completely dissolve the monomers, several drops of methylene chloride were added.

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49 UV-Vis examination of these D-A-D monomer systems shows that a dramatic red shift occurs upon increasing acceptor strength. For example, EDOT and pyridine have l max values near 260 nm, yet the resulting monomer created by coupling them gives a l max near 350 nm. This 90 nm red shift not only results from creation of a highly functionalized monomer, but is also due to its D-A nature. By coupling the pyrido[3,4b ]pyrazine unit with EDOT, the l max values red shift approximately 200 nm to 480 nm. Upon polymerization to create highly conjugated polymers, the UV-Vis absorptions are expected to also dramatically shift to the red to a series of low band gap polymers. 3.5 Experimental 3.5.1 General Methods All syntheses were conducted under an argon atmosphere unless otherwise noted. Tetran -butylammonium perchlorate was synthesized via the metathesis of perchloric acid and tetran -butylammonium bromide and recrystallized using i -propanol. n -Butyllithium ( n -BuLi) was titrated prior to use with N -pivaloylo -toluidine. 37 3,4Ethylenedioxythiophene was distilled from calcium hydride and stored frozen until used. Thiophene was distilled from potassium hydroxide. Tetrahydrofuran and diethyl ether were distilled from sodium/potassium-benzophenone ketyl or used from an Aldrich PurePac system after being passed through an activated alumina column. Methanol was distilled from magnesium. Toluene was distilled from sodium/potassium-benzophenone ketyl. N -bromosuccinimide was recrystallized from water. 37. Suffert, J. J. Org. Chem. 1989 , 54 , 509-510.

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50 3.5.2 Analytical Methods 1 H and 13 C NMR spectra were collected using either a Varian Mercury 300 or Varian Gemini 300 spectrometer. High resolution mass spectrometry was obtained using a Finnigan MAT95Q (fast atom bombardment ionization) and was performed by the Mass Spectrometry Core Laboratory at the University of Florida. Microelemental analyses were performed by the University of Florida using an EA1108 Elemental Analyzer. UV-VisNIR experiments were performed using a Varian-Cary 5E spectrophotometer. Uncorrected melting points were obtained using a capillary apparatus. Thin layer chromatography was performed on Whatman silica gel plates (250 m m silica gel 60 , fluorescent indicator UV254). All NMR and UV-Vis data is summarized in Appendix A. 3.5.3 X-ray crystallography Data for BEDOT-PyrPyr-Ph 2 was collected at 173 K on a Siemens SMART PLATFORM equipped with a CCD area detector and a graphite monochromator utilizing MoK a radiation ( l = 0.71073 ). Cell parameters were refined using up to 8192 reflections. A full sphere of data (1850 frames) was collected using the w -scan method (0.3 frame width). The first 50 frames were remeasured at the end of data collection to monitor instrument and crystal stability (maximum correction on I was < 1%). Absorption corrections by integration were applied based on measured indexed crystal faces. The structure was solved by the Direct Methods in SHELXTL5, and refined using full-matrix least squares. 38 The non-H atoms were treated anisotropically, whereas the hydrogen atoms were calculated in ideal positions and were riding on their respective 38. Sheldrick, G. M. SHELXTL6 . Bruker-AXS, Madison, Wisconsin, USA, 2000 .

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51 carbon atoms. The space group, P212121, is chiral thus only one enantiomer exists in the crystal. The correct enantiomer is reported here judging by the value of a Flack parameter of -0.02(11). A total of 361 parameters were refined in the final cycle of refinement using 13405 reflections with I > 2 s (I) to yield R 1 and wR 2 of 5.32% and 11.92%, respectively. Refinement was done using F 2 . All crystal structure data is tabulated in Appendix B. 3.5.4 Donor Synthesis (2,3-Dihydro-thieno[3,4b ][1,4]dioxin-5-yl)-trimethyl-stannane (2) 9 : In a 500 mL three-necked round bottom flask equipped with a stir bar, 40.5 mL of n -butyllithium (2.5 M in hexanes, 110 mmol) was added to stirred solution of 3,4-ethylenedioxythiophene (14.4 g, 101 mmol) dissolved in 100 mL anhydrous THF cooled to -78 C. After one and a half hours, 111 mL of 1.0 M trimethylstannyl chloride (111 mmol) was added. The reaction mixture was allowed to warm to room temperature overnight. Removal of the THF under reduced pressure resulted in the formation of a pink solid. Water (100 mL) was added, and the slurry was extracted with pentane. After drying the combined organic layers with magnesium sulfate, the solvent was removed under reduced pressure to give a white solid. The crude solid was melt distilled under vacuum to give 30.9 g (99.9%) of (2,3dihydro-thieno[3,4b ][1,4]dioxin-5-yl)-trimethyl-stannane as a white wax. mp 48-50 C. 1 H NMR (300 MHz, CDCl 3 ): d 0.36 (s, 9H), 4.17 (s, 4H), 6.58 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ): d -8.62, 64.63, 64.69, 105.74, 109.06, 142.48, 147.81. Anal. Calcd. for C 9 H 14 O 2 SSn: C, 35.44; H, 4.63; O, 10.49; S, 10.51; Sn, 38.92. Found: C, 35.57; H, 4.69; S, 10.89. HRMS calcd for C 9 H 14 O 2 SSn (M + ), 305.9737; found, 305.9746.

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52 Trimethyl-(7-trimethylstannanyl-2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)silane (4) : 5.00 g (0.0352 mol) of freshly distilled EDOT and 150 mL anhydrous THF were combined in a 250 mL three-necked round bottom flask equipped with a stir bar. After cooling the above solution to -78 C, 14.2 mL of n -butyllithium (2.5 M in hexanes) was added via syringe. After 90 minutes, 4.4 mL (0.35 mol) of trimethylsilyl chloride was syringed and the reaction mixture was allowed to warm to room temperature for one hour. The reaction mixture was then cooled to -78 C, and another 14.2 mL portion of 2.5 M n butyllithium was added. After 90 minutes, 35.2 mL of 1 M (0.0352 mol) trimethylstannyl chloride was added, and the reaction was stirred overnight at room temperature to give a clear yellow solution. The reaction mixture was concentrated to approximately 20% of the original volume under reduced pressure and poured into 100 mL of water. The aqueous phase was extracted with pentane. The pentane layers were combined and dried with magnesium sulfate. The solvent was then removed under reduced pressure to give 12 g (88%) of trimethyl-(7-trimethylstannanyl-2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)silane as a white wax. mp 64-65 C. 1 H NMR (300 MHz, CDCl 3 ): d 0.31 (s, 9H), 0.37 (s, 9H), 4.18 (m, 4H). 13 C NMR (75 MHz, CDCl 3 ): d -8.67, -0.70, 64.45, 64.68, 104.67,152.59, 147.90. Anal. Calcd. for C 12 H 22 O 2 SSiSn: C, 38.21; H, 5.88; O, 8.48; S, 8.50; Si, 7.45; Sn, 31.47. Found: C, 37.93; H, 5.74; S, 8.70. HRMS calcd for C 12 H 22 O 2 SSiSn (M + ), 378.0131; found, 378.0131. 2,3,4,5-Tetrabromothiophene (5) 10 : In a four liter three-necked round bottom flask equipped with a stir bar and reflux condenser, a one liter equilibrium addition funnel, and vented to a scrubber charged with a saturated sodium hydroxide solution was added 500 g (5.95 mol) of thiophene and 180 mL chloroform. After cooling to 0 C with an ice

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53 bath, bromine (2.38 kg, 1.31 L, 25.6 mol) was added dropwise over a 12 hour period. The deep red solution was observed to give off hydrobromic acid that was trapped by the scrubber, but no bromine was seen to escape. Upon the final addition of the bromine, the reaction was allowed to warm to room temperature under constant stirring. After 12 hours, the reaction became an intractable red-orange solid, which was broken into chunks with a large metal spatula and saturated sodium hydroxide solution was added until an alkaline pH was reached. A minimal amount of a saturated sodium thiosulfate solution was added to remove any residual bromine (disappearance of any orange in the reaction mixture). Washing with cold acetone gave 1.72 kg of 2,3,4,5-tetrabromothiophene as a white crystalline solid (72.6% yield). mp 119-120 C. 13 C NMR (75 MHz, CDCl 3 ): d 110.25, 116.89. 3,4-Dibromothiophene (6) [11] : 2,3,4,5-Tetrabromothiophene (107.6 g, 0.2692 mol) was dissolved in 500 mL THF in a one liter three-necked round botton flask equipped with a stir bar. Upon cooling to -78 C, 215 mL (0.538 mol) n -butyllithium (2.5 M in hexanes) was added dropwise via an addition funnel. Upon completion of this addition, the reaction mixture was immediately poured onto ice. The solution was then extracted with chloroform, and the combined organic layers were dried with magnesium sulfate. A black viscous oil resulted after removal of the chloroform under reduced pressure. Vacuum distillation gave 53.7 g (83.1%) of 3,4-dibromothiophene as a clear oil. bp 109 C, 15 mm Hg. 1 H NMR (300 MHz, CDCl 3 ): d 7.29 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ): d 113.81, 123.68. 3,4-Dimethoxythiophene (7) [13] : Sodium methoxide was prepared by careful addition of 50 g (2.1 mol) of sodium to one liter of freshly distilled methanol in a three-

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54 necked round bottom flask equipped with a stir bar and reflux condenser. To the sodium methoxide was added 100 g (0.413 mol) 3,4-dibromothiophene, 32.9 g (0.413 mol) copper (II) oxide, and 1.37 g (0.00827 mol) potassium iodide. After refluxing for three days, the reaction mixture was allowed to cool and then filtered through a sintered glass frit. Upon pouring into water, the purple-red solution was extracted with ether. The ether layers were dryed with magnesium sulfate and removed under reduced pressure to give a yellow liquid. Vacuum distillation gave 38 g (64%) of 3,4-dimethoxythiophene as a clear, colorless oil. bp 133 C, 15 mm Hg. 1 H NMR (300 MHz, CDCl 3 ): d 3.79 (s, 6H), 6.13 (s, 2H). 13 C NMR (75 MHz, CDCl 3 ): d 57.15, 95.97, 147.46. 3,3-Dimethyl-3,4-dihydro-2 H -thieno[3,4b ][1,4]dioxepine (8) 4 : In a one liter three-necked round bottom flask equipped with a stir bar, a Soxhlet extractor charged with 4 sieves, and a reflux condenser was charged with 16.6 g (0.116 mol) 3,4dimethoxythiophene, 24.2 g (0.143 mol) neopentyl glycol, 2.20 g p -toluenesulfonic acid monohydrate, and 600 mL of freshly distilled toluene. The reaction mixture was heated to reflux for 24 hours. Upon cooling to room temperature, the reaction mixture was poured into a two liter separatory funnel, and 500 mL of water was added. The toluene layer was separated, dried with MgSO 4 , and removed under reduced pressure to yield a yellow solid. Column chromatography (silica, hexanes/DCM, 3:2) gave 13.0 g of 3,3-dimethyl-3,4dihydro-2 H -thieno[3,4b ][1,4]dioxepine as a white crystalline solid (60.9% yield). TLC (silica, methylene chloride) R f 0.69. mp 49-51 C. 1 H NMR (300 MHz, CDCl 3 ): d 1.02 (s, 6H), 3.73 (s, 4H), 6.47 (s, 2H). 13 C NMR (75 MHz, CDCl 3 ): d 21.63, 38.83, 80.03, 105.46, 149.96.

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55 2,5-Bis-trimethylsilanyl-thiophene (9) 16 : In a 500 mL three-necked round bottom flask equipped with a stir bar, 35 mL (0.44 mol) thiophene was dissolved in 300 mL anhydrous THF. Upon cooling to -78 C, 175 mL (0.44 mol) of n -butyllithium (2.5 M in hexanes) was added dropwise via a equilibrium addition funnel. After one hour, 56 mL (0.44 mol) of chlorotrimethylsilane was added dropwise via syringe, and the reaction mixture was allowed to warm to room temperature for 90 minutes. The reaction was cooled once again to -78 C, and another 175 mL portion of n -butyllithium solution was added dropwise. After 90 minutes, 56 mL of chlorotrimethylsilane was added dropwise, and the reaction mixture was allowed to warm to room temperature overnight. The solution was filtered through a sintered glass frit to remove any precipitated salts, and the resulting solution was poured into water. The resulting precipitate was extracted with ether. After drying the combined organic extracts with calcium chloride, the solvent was removed under reduced pressure to obtain a light yellow oil. Vacuum distillation gave 59.6 g (59.6%) of 2,5-bis-trimethylsilanyl-thiophene as a colorless oil. bp 62 C, 15 mm Hg. 1 H NMR (300 MHz, CDCl 3 ): d 0.38 (s, 18H), 7.38 (s, 2H). 13 C NMR (75 MHz, CDCl 3 ): d 0.09, 135.06, 145.77. 3.5.5 Acceptor Synthesis 2,3-Diphenyl-pyrido[3,4b ]pyrazine (10) 18 : In a 50 mL round bottom flask equipped with a stirbar and a reflux condenser was added 2.00 g (0.0183 mol) 3,4diaminopyridine, 4.23 g (0.0201 mol) benzil, and 20 mL n -butanol. After refluxing for 48 hours, the reaction mixture was allowed to cool, and the pale yellow solid that resulted was filtered and washed with water. Purification using column chromatography (silica gel, ethyl acetate) gave 4.50 g of 2,3-diphenyl-pyrido[3,4b ]pyrazine as a white solid (86.9%).

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56 mp 181-182 C. 1 H NMR (300 MHz, CDCl 3 ): d 7.31 7.55 (m, 10H), 7.97 (dd, J = 0.95 Hz, J = 5.7 Hz, 1 H), 8.81, (d, J = 5.7 Hz, 1H), 9.59 (d, 1H, J = 0.95 Hz). 13 C NMR (75 MHz, CDCl 3 ): d 121.25, 128.33, 129.32, 129.60, 129.71, 128.78, 136.20, 138.19, 143.47, 147.26, 154.38, 155.26, 157.83. 2,5-Dibromopyridine-3,4-diamine (11) [1]d : 3,4-Diaminopyridine (17.9 g, 0.164 mol) was combined with 250 mL of 47% hydrobromic acid in a 500 mL three-necked round bottom flask equiped with a stir bar and reflux condenser. The 3,4-diaminopyridine dissolved upon heating to reflux, and 17 mL (0.33 mol) of bromine was added dropwise. After refluxing for 15 hours, the reaction mixture was allowed to cool resulting in a cream precipitate resulted. The solid was collected by filtration and alternatingly washed with solutions of sodium thiosulfate and potassium carbonate. The cream colored powder was then washed with water and dried in a vacuum desiccator over silica to give 41.5 g (94.7%) of 2,5-dibromopyridine-3,4-diamine. mp 218-220 C. 1 H NMR (300 MHz, DMSOd 6 ): d 5.04 (s, 2H), 5.98 (s, 2H), 7.52 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ): d 104.51, 125.96, 128.85, 138.44, 139.23. 5,8-Dibromopyrido[3,4b ]pyrazine (12) : In a 50 mL round bottom flask equipped with a stirbar and reflux condenser, 2,5-dibromopyridine-3,4-diamine (0.44 g, 1.6 mmol) was dissolved in 25 mL of n -butanol. Glyoxal was added (1.0 mL, 8.7 mmol), and the reaction mixture was refluxed for five hours. After cooling, the yellow precipitate was collected by filtration. Column chromatography (silica gel, CHCl 3 eluant) gave 1.6 g (80%) of 5,8-dibromopyrido[3,4b ]pyrazine as a white solid. TLC (silica, methylene chloride) R f x.xx. mp 175-177 C. 1 H NMR (300 MHz, CDCl 3 ): d 8.87 (s, 1H), 9.21 (d, 1H), 9.29 (d, 1H). 13 C NMR (75 MHz, CDCl 3 ): d 120.67, 138.32, 147.94, 148.06, 150.30.

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57 5,8-Dibromo-2,3-diphenyl-pyrido[3,4b ]pyrazine (13) [1]d : In a 100 mL round bottom flask equipped with a stirbar and a reflux condenser, 25 mL of n -butanol and 3.00 g (11.2 mmol) of 2,5-dibromopyridine-3,4-diamine were combined. Benzil (2.10 g, 10.0 mmol) was added, and the reaction mixture was brought to reflux for 24 hours. After cooling, the resulting solid that formed was collected by vacuum filtration. Recrystallization from ethanol, followed by column chromatography (silica, DCM eluant), gave 1.69 g (38%) of 5,8-dibromo-2,3-diphenyl-pyrido[3,4b ]pyrazine as a white solid. TLC (silica, methylene chloride) R f 0.71. mp 215-216 C. 1 H NMR (300 MHz, CDCl 3 ): d 7.39 (m, 6H), 7.64 (m, 4H), 8.74 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ): d 120.09, 128.46, 130.01, 130.22, 130.39, 135.80, 137.08, 137.15, 142.32, 146.15, 147.09, 156.06, 158.24. 3-Amino-pyrazine-2-carboxylic acid methyl ester (14) [21] : 3-Aminopyrazinoic acid (25.0 g, 0.180 mol) was dissolved in 125 mL (3.09 mol) of methanol. After cooling in an ice bath, 32 mL of concentrated sulfuric acid was slowly added. After stirring for two days, the solution was poured into water, and a saturated sodium carbonate solution was added until the pH became slightly alkaline. The resulting solid was collected by filtration and decolorized in water with activated carbon. Recrystallization from water gave 11.0 g (39.8%) of 3-amino-pyrazine-2-carboxylic acid methyl ester as a white solid. mp 168-169 C. 1 H NMR (300 MHz, CDCl 3 ): d 3.96 (s, 3H), 6.52 (s, 2H), 7.97 (d, 1H, J = 2 Hz), 8.18 (d, 1H, J = 2 Hz). 13 C NMR (75 MHz, CDCl 3 ): d 52.75, 124.22, 133.50, 147.48, 155.84, 166.72. 3-Amino-6-bromo-pyrazine-2-carboxylic acid (16) [22] : 3-Amino-pyrazine-2carboxylic acid methyl ester (5.00 g, 0.0326 mol) was dissolved in 27 mL of warm glacial acetic acid. To this solution, 1.8 mL of bromine was added dropwise. Upon completion of

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58 the bromine addition, the reaction mixture was allowed to stand for one and a half hours followed by addition of 40 mL of water. A solution of sodium hydroxide (18 g in 30 mL water) was added to saponify the ester, and the solution was refluxed for 15 minutes. The reaction mixture was treated with decolorizing charcoal, filtered, and allowed to cool. The brown solid that resulted was collected by filtration and dried under vacuum to give 1.90 g of the crude sodium salt of the title compound. The salt was then dissolved in 52 mL warm water, and the solution was then acidified by addition of 1.3 mL of 48% hydrobromic acid. The solution was then cooled to give brown crystals that were then collected and dried under vacuum. Recrystallization from water gave 1.47 g (20.6%) of 3-amino-6-bromopyrazine-2-carboxylic acid as pale, yellow needles. mp 188 C (violent decomposition). 1 H NMR (300 MHz, d 6 -DMSO): d 3.34 (s, 2H), 7.55 (s, 2H, hydrated acid), 8.38 (s, 1H). 13 C NMR (75 MHz, d 6 -DMSO): d 122.41, 123.27, 149.60, 155.14, 166.87. 5-Bromo-pyrazin-2-ylamine (17a) [22] : In a 50 mL round bottom flask equipped with a stirbar and reflux condenser, 3-amino-6-bromo-pyrazine-2-carboxylic acid (1.30 g, 0.00600 mol) was carefully added to 13 mL of boiling tetralin. The reaction continued for 30 minutes as the vigorous bubbling slowed. The reaction was then allowed to cool overnight and filtered to give crude yellow crystals. After washing with petroleum ether, the solid was dried under vacuum and recrystallized from dichloromethane followed by column chromatography (silica, 9:1 DCM-acetonitrile) to give 0.40 g (40%) of 5-bromopyrazin-2-ylamine as a white solid. TLC (silica, 9:1 methylene chloride-acetonitrile) R f 0.27. mp 111-112 C. 1 H NMR (300 MHz, CDCl 3 ): d 4.73 (s, 2H), 7.75 (s, 1H, J = 1.43 Hz), 8.06 (s, 1H, J = 1.43 Hz). 13 C NMR (75 MHz, CDCl 3 ): d 126.97, 131.79, 144.13, 153.42.

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59 5-Bromo-pyrazin-2-ylamine (17b) [23] : Dichloromethane (300 mL) was cooled to 0 C in a jacketed one liter reactor equipped with a stir bar. 2-Aminopyrazine (5.00 g, 0.0526 mol) was added and allowed to dissolve. N -Bromosuccinimide was added (9.4 g, 0.053 mol), and the reaction mixture was stirred for six hours. The reaction was then poured into a separatory funnel and washed four times with a saturated sodium carbonate solution and once with water. The organic layer was then dried with magnesium sulfate before solvent removal under reduced pressure to give an orange solid. Recrystallization from methylene chloride followed by column chromatography (silica, 9:1 DCM:acetonitrile) gave 3.00 g (33.3%) of 5-bromo-pyrazin-2-ylamine as a white solid. TLC (silica, 9:1 methylene chloride-acetonitrile) R f 0.27. mp 111-112 C. 1 H NMR (300 MHz, CDCl 3 ): d 4.73 (s, 2H), 7.75 (s, 1H, J = 1.43 Hz), 8.06 (s, 1H, J = 1.43 Hz). 13 C NMR (75 MHz, CDCl 3 ): d 126.97, 131.79, 144.13, 153.42. 3-Chloropyrazine-1-oxide (21) [28] : In a 100 mL three-necked round bottom flask equipped with a stir bar and a reflux condenser, 13.8 g (0.120 mol) 2-chloropyrazine and 36 mL glacial acetic acid were combined. Hydrogen peroxide (24 mL) was carefully added, and the reaction was heated to 75C for 24 hours. Upon cooling, the solution was brought to a pH of 9 by the addition of a saturated sodium carbonate solution. After extraction with chloroform, the organic layers were combined, washed with saturated sodium chloride solution, and dried with magnesium sulfate. Removal of the chloroform gave a white solid that was recrystallized from ethanol to give 9.01 g (57.4%) of 3chloropyrazine-1-oxide. mp 94-95 C. 1 H NMR (300 MHz, CDCl 3 ): d 8.02 (dd, J = 1.46 Hz, J =4.38 Hz, 1H), 8.15 (dd, J = 1.46 Hz, 1H), 8.25 (d, J = 4.38 Hz, 1H). 13 C NMR (75 MHz, CDCl 3 ): d 133.42, 133.74, 146.20, 152.00.

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60 2,5-Dichloropyrazine (22) [27] : In a 50 mL round bottom flask equipped with a stirbar, phosphorus oxychloride (7.85 mL, 0.0858 mol) was warmed to 60 C. 3-Chloropyrazine-1-oxide was carefully added dropwise, and the reaction was slowly heated to reflux. At ~75 C, the reaction began to bubble vigorously. After one hour, the reaction was allowed to cool in an ice bath and then was poured onto crushed ice. Extraction with chloroform resulted in a yellow solution. The chloroform was removed under reduced pressure after drying with magnesium sulfate. Distillation (15 mm Hg, 67 C) resulted in two spots on TLC. The crude product was then purified on a silica gel column with methylene chloride as the eluant to give 2.27 g (52.5%) of a 1:1 mixture of 2,5dichloropyrazine and 2,6-dichloropyrazine as a clear liquid. mp ~0 C. bp 67 C, 15 mm Hg. 1 H NMR (300 MHz, CDCl 3 ): d 8.28 (s, 1H), 8.47 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ): d 141.64, 142.29. 3.5.6 Donor-Acceptor Monomer Synthesis 2,5-Bis-(2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)-pyridine (1) [32] : 100 mL of anhydrous THF was added to a 500 mL three-necked round bottom flask equipped with a stirbar and a reflux condenser that had previously been flame dried under vacuum. 3,4Ethylenedioxythiophene (5.00 g, 0.0352 mol) was added via syringe. Upon cooling of the solution to -78 C, 14.1 mL of n -butyllithium was added (2.5 M in hexanes). After one hour, 35.2 mL of a 1.0 M solution of ZnCl 2 was added via syringe, and the solution was warmed to 0 C for one hour. The reaction mixture was allowed to warm to 0 C for one hour, and a solution of 2,5-dibromopyridine (2.78 g, 0.0117 mol) and tetrakis(triphenylphosphine)palladium (0) (100 mg) in 25 mL THF was added dropwise. The reaction mixture was heated to reflux for 72 hours, cooled, and poured into water. The THF

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61 was removed under reduced pressure, and the resulting yellow solid was filtered. Recrystallization (THF-water) followed by column chromatography (silica, xxx eluant) gave 3.78 g of 2,5-bis-(2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)-pyridine as a canary yellow solid (90%). mp 178-179 C. UV-Vis (methylene chloride) l max ( e ) 350 (36 000) nm. 1 H NMR (300 MHz, CDCl 3 ): d 4.30 (m, 8H), 6.33 (s, 1H), 6.42 (s, 1H), 7.91 (m, 2H), 8.90 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ): d 64.56, 64.62, 64.98, 65.22, 98.51, 101.38, 114.35, 119.12, 120.06, 126.97, 133.08, 139.19, 139.99, 142.26, 142.49, 146.55, 149.35. Anal. calcd for C 17 H 13 NO 4 S 2 : C, 56.81; H, 3.65; N, 3.90; O, 17.81; S, 17.81. Found: C, 56.90; H, 3.72; N, 3.85. HRMS calcd for C 17 H 13 NO 4 S 2 (M+H), 360.0364; found, 360.0352. 5,8-Bis-(2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)-pyrido[3,4b ]pyrazine (25) : A portion of TMS-BEDOT-PyrPyr was de-silylated during purification on a silica gel column to give 0.030 g of 5,8-bis-(2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)-pyrido[3,4b ]pyrazine as a bright red solid. TLC (silica, ethyl acetate) R f 0.5. 1 H NMR (300 MHz, CDCl 3 ): d 4.29-4.46 (m, 8H), 6.58 (s, 1H), 6.67 (s, 1H), 8.97 (d, J = 1.43 Hz, 1H), 9.06 (d, J = 1.43 Hz, 1H), 9.72 (s, 1H). 5,8-Bis(2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)-2,3-diphenyl-pyrido[3,4b ]pyrazine (3) [32]a : 5,8-Dibromo-2,3-diphenyl-pyrido[3,4b ]pyrazine (1.00 g, 2.40 mmol) and (2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)-trimethyl-stannane (2.867 g, 9.04 mmol) were combined in a 50 mL round bottom flask equipped with a stirbar. Anhydrous DMF (25 mL) was added along with 0.159 g (10 mol%) trans dichlorobis(triphenylphosphine)palladium (II). After warming to 75 C for 24 hours, the reaction mixture was allowed to cool and the mixture was poured into 200 mL of water.

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62 The red solid was collected by vacuum filtration. Column chromatography (silica gel, 1:1 methylene chloride-ethyl acetate) gave 0.920 g (68%) of dark red needles of 5,8-bis(2,3dihydro-thieno[3,4b ][1,4]dioxin-5-yl)-2,3-diphenyl-pyrido[3,4b ]pyrazine. mp 295-297 C. TLC (silica, 1:1 methylene chloride-ethyl acetate) R f 0.5. UV-Vis (methylene chloride) l max ( e ) 272 (190 000), 325 (340 000), 478 (100 000) nm. 1 H NMR (300 MHz, CDCl 3 ): d 4.40 (m, 8H), 6.58 (s, 1H), 6.67 (s. 1H), 7.39 (m, 6H), 7.74 (m, 4H), 9.76 (s, 1H). 13 C NMR (75 MHz, CDCl3): d 64.25, 64.32, 64.86, 65.38, 103.66, 105.90, 110.74, 122.42, 128.29, 129.31, 129.64, 130.34, 130.52, 132.30, 137.94, 138.06, 139.27, 140.72, 141.39, 142.83, 145.16, 150.22, 152.20, 154.89. Anal. calcd for C 9 H 12 O 2 S: C, 66.06; H, 3.76; N, 7.46; S, 11.38. Found: C, 66.22; H, 3.89; N, 7.67; S, 11.45. HRMS calcd for C 31 H 22 O 4 N 3 S 2 (M+H), 564.1052; found, 564.1052. 2,3-Diphenyl-5,8-bis-(7-trimethylsilanyl-2,3-dihydro-thieno[3,4b ][1,4]dioxin5-yl)-pyrido[3,4b ]pyrazine (26) : 5,8-Dibromo-2,3-diphenyl-pyrido[3,4b ]pyrazine (0.500 g, 1.13 mmol) and trimethyl-(7-trimethylstannanyl-2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)-silane (0.894 g, 2.37 mmol) were combined in a 50 mL round bottom flask equipped with a stirbar. 25 mL of anhydrous DMF was added along with 0.158 g (10 mol%) trans-dichlorobis(triphenylphosphine)palladium (II). After warming to 75 C for 24 hours, the reaction mixture was allowed to cool. The mixture was poured into 200 mL of water, and the red precipitate was collected by vacuum filtration. Column chromatography (silica gel, 3:1 hexanes:ethyl acetate eluant) gave 0.467 g (77%) of 2,3diphenyl-5,8-bis-(7-trimethylsilanyl-2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)pyrido[3,4b ]pyrazine as a bright red solid. TLC (reverse phase C18F silica, 6:1 methanolethyl acetate) R f 0.36. mp 243-244 C. 1 H NMR (300 MHz, CDCl 3 ): d 0.38 (s, 9H), 0.39

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63 (s, 9H), 4.35 (m, 8H), 7.37 (m, 6H), 7.85 (m, 4H), 9.82 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ): d -0.61, -0.53, 64.38, 64.44, 64.86, 64.39, 77.43, 115.39, 115.62, 118.11, 118.96, 122.59, 128.42, 128.44, 129.61, 129.97, 130.71, 130.94, 132.56, 138.28, 138.45, 139.48, 141.62, 143.47, 144.72, 145.24, 147.05, 147.40, 150.35, 152.06, 154.71. 2,5-Bis-(7-trimethylsilanyl-2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)pyridine (27) : 2,5-Dibromopyridine (0.500 g, 2.11 mmol) and trimethyl-(7trimethylstannanyl-2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)-silane (1.60 g, 4.22 mmol) were combined in a 50 mL round bottom flask equipped with a stirbar. 25 mL of anhydrous DMF was added along with 0.15 g (10 mol%) trans dichlorobis(triphenylphosphine)palladium (II). After warming to 75 C for 24 hours, the reaction mixture was allowed to cool. The mixture was poured into 200 mL of water, and the red precipitate was collected by vacuum filtration. Purification was attempted with column chromatography, recrystallization, and reverse phase HPLC. TLC (reverse phase C18F silica, 6:1 methanol-ethyl acetate) R f 0.36. 5,8-Bis-(7-trimethylsilanyl-2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)pyrido[3,4b ]pyrazine (28) : 5,8-Dibromopyrido[3,4b ]pyrazine (0.100 g, 0.346 mmol) and trimethyl-(7-trimethylstannanyl-2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)-silane (0.260 g, 0.692 mmol) were combined in a 50 mL round bottom flask equipped with a stirbar. Anhydrous DMF (25 mL) was added along with 0.017 g (10 mol%) trans dichlorobis(triphenylphosphine)palladium (II). After warming to 75 C for 24 hours, the reaction mixture was allowed to cool. The mixture was poured into brine and extracted three times with 100 mL of chloroform. The organic layers were combined and washed five times with 200 mL of water. After drying with magnesium sulfate, the chloroform was

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64 removed under reduced pressure to give a dark red solid. Column chromatography (passivated silica gel, 3:2 ethyl acetate:hexanes eluant) gave 0.090 g (44%) dark red needles of 5,8-bis-(7-trimethylsilanyl-2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)pyrido[3,4b ]pyrazine. 2,5-Bis-(3,3-dimethyl-3,4-dihydro-2 H -thieno[3,4b ][1,4]dioxepin-6-yl)pyridine (29) : ProDOT-Me 2 was dissolved in 50 mL of anhydrous THF in a 250 mL threenecked round bottom flask equipped with a stir bar and a reflux condenser. Upon cooling to -78 C, n -butyllithium was added. After one hour, zinc (II) chloride was added, and the reaction was allowed to warm to 0 C for one hour. A solution of 2,5-dibromopyridine and Pd(PPh 3 ) 4 was added and the reaction was refluxed 3 hours. After cooling, the reaction mixture was poured into water, and the resulting solid was filtered. Column chromatography twice using 3:2 dichloromethane-hexanes followed by dichloromethane gave 4.54 g f 2,5-bis-(3,3-dimethyl-3,4-dihydro-2 H -thieno[3,4b ][1,4]dioxepin-6-yl)pyridine as a bright yellow solid (50.4%). TLC (silica, methylene chloride) R f 0.5. mp 182184 C. UV-Vis (solvent) l max ( e ) 356 (590 000) nm. 1 H NMR (300 MHz, CDCl 3 ): d 1.06 (s, 1H), 1.08 (s, 1H), 3.80 (s, 2H), 3.81 (s, 2H), 3.84 (s, 2H), 3.92 (s, 2H), 6.48 (s, 1H), 6.56 (s, 1H), 7.90 (dd, 1H, J = 2.38 Hz, J = 8.56 Hz), 8.03 (dd, 1H, J = 0.95 Hz, J = 8.56 Hz), 8.90 (d, 1 H, J = 2.38 Hz). 13 C NMR (75 MHz, CDCl 3 ): d 22.03, 22.11, 29.65, 39.11, 80.06, 80.09, 80.10, 80.21, 103.97, 106.81, 119.14, 120.25, 123.55, 127.44, 133.79, 147.01, 147.97, 149.82, 150.54, 150.82. HRMS calcd for C 23 H 26 NO 4 S 2 (M+H), 444.1303; found, 444.1303. Anal. calcd for C 23 H 26 NO 4 S 2 : C, 62.28; H, 5.68; N, 3.16; O, 14.43; S, 14.46. Found: C, 59.90; H, 5.46; N, 3.02.

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65 5,8-Bis-(3,3-dimethyl-3,4-dihydro-2 H -thieno[3,4b ][1,4]dioxepin-6-yl)-2,3diphenyl-pyrido[3,4b ]pyrazine (30) : In a 100 mL three-necked round bottom flask equipped with a stirbar, 50 mL of THF and 0.87 g (0.0047 mol) ProDOT-Me 2 were combined. The solution was then cooled to -78 C. 2.4 mL (0.0047 mol) of 2.5 M n butyllithium was added. After one hour, 4.8 mL (0.0047 mol) of 1.0 M zinc chloride was added ,and the reaction was warmed to 0 C for one hour. In a separate 250 mL threenecked round bottom flask equipped with a stirbar, 5,8-dibromo-2,3-diphenyl-pyrido[3,4b ]pyrazine (1.04 g, 0.0024 mol), and 0.010 g tetrakis -triphenylphosphine palladium (0) were dissolved in 50 mL THF. After heating this mixture to reflux, the ProDOT-Me 2 zincate complex was added dropwise. After refluxing for one day, the reaction was cooled, poured into water, and extracted with methylene chloride. The organic phases were combined, dried with magnesuim sulfate, and removed under reduced pressure to give a red orange solid. Column chromatography (silica, 19:1 methylene chloride-acetonitrile) gave 1.01 g of 5,8-bis-(3,3-dimethyl-3,4-dihydro-2 H -thieno[3,4b ][1,4]dioxepin-6-yl)-2,3diphenyl-pyrido[3,4b ]pyrazine as a red-orange solid. TLC (silica, 19:1 methylene chloride-acetonitrile) R f 0.5. mp 258-260 C. UV-Vis (solvent) l max ( e ) 264 (220 000), 312 (290 000), 445 (91 000) nm. 1 H NMR (300 MHz, CDCl 3 ): d 0.96 (s, 6H), 1.06 (s, 6H), 3.57 (s, 2H), 3.84 (s, 2H), 3.87 (s, 2H), 3.78 (s, 2H), 6.73 (s, 1H), 6.81 (s, 1H), 7.37 (m, 6H), 7.67 (m, 4H), 9.56 (s, 1H). 13 C NMR (75 MHz, CDCl 3 ): d 21.51, 21.80, 38.72, 38.79, 79.91, 79.99, 80.18, 80.44, 108.51, 109.21, 115.09, 123.81, 128.14, 128.20, 129.13, 129.58, 130.17, 130.51, 133.21, 137.98, 138.54, 145.90, 149.73, 149.82, 150.51, 152.89, 155.27. HRMS calcd for C 37 H 34 N 3 O 4 S 2 (M+H), 648.1991; found, 648.1991. Anal. calcd

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66 for C 37 H 34 N 3 O 4 S 2 : C, 68.60; H, 5.13; N, 6.49; O, 9.88; S, 9.90. Found: C, 68.11; H, 5.16; N, 6.15.

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67 CHAPTER 1 D-A-D POLYMER ELECTROCHEMISTRY AND OPTICAL PROPERTIES 1.1 Introduction The previous chapter discussed the synthesis and analytical characterization of a family of donor-acceptor-donor (D-A-D) monomers based on alternating alkylendioxythiophene donors and nitrogen-based heterocycle acceptors. This chapter will describe the electrochemical and optical properties of this family with an emphasis on the two monomers shown in Figure 4-1. Polymers synthesized electrochemically from monomers 1 and 2 have unique properties when reductively, or n-type, doped and a full examination of cation electrolyte effects are studied herein. Several groups are actively pursuing n-doping, 1 and the work in this chapter describes how assigning the claim of ndoping to an electrochemical reduction can be inaccurate. In addition to cyclic voltammetry, the properties of these systems are examined using differential pulse voltammetry, in-situ conductance, spectroelectrochemistry, and colorimetry in order to classify a system as n-type dopable. 1. (a) Aizawa, M.; Watanabe, S.; Shinohara, H.; Shirakawa, H. J. Chem. Soc., Chem. Commun. 1985 , 264-265. (b) Arbizzani, C.; Mastragostino, M.; Soavi, F. Electrochim. Acta 2000 , 45 , 2273-2278. (c) Gregg, B. A.; Cormier, R. A. J. Phys. Chem. B 1998 , 102 , 9952-9957. (d) Jow, T. R.; Shacklette, L. W. J. Electrochem. Soc. 1988 , 135 , 541-548. (e) Murase, I.; Ohnishi, T.; Noguchi, T.; Hirooka, M. Polym. Commun. 1984 , 25 , 327. (f) Sato, M.; Tanaka, S.; Kaeriyama, K. J. Chem. Soc., Chem. Commun. 1987 , 1725-1726. (g) Schenk, R.; Gregorius, H.; Mllen, K. Adv. Mater. 1991 , 3 , 492-493.

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68 In addition to monomers 1 and 2 , monomers 3 through 8 , shown in Figure 4-2, were also studied in this chapter. However, their electrochemical and optical properties are inferior due to the inability to adequately purify the monomers prior to electropolymerization or insolubility problems of the monomers in electrochemical solvents. 4.2 Electropolymerization Electropolymerization of compound 1 was carried out using cyclic voltammetry from a 5 mM BEDOT-Pyr/0.1 M tetran -butylammonium perchlorate/acetonitrile solution. Several drops of methylene chloride were added to achieve complete dissolution of the monomer due to its limited solubility in acetonitrile. As shown in Figure 4-3, monomer 1 oxidizes at a bare platinum electrode with a peak (E p,m ) of 1.1 V vs SCE. Upon continued cycling between +0.1 and 1.15 V, a current density increase can be seen between +0.3 V and +1.0 V that corresponds to the redox activity of the polymer being formed on the electrode surface. At higher potentials, the current density also increases due to further monomer oxidation as deposition of polymer occurs. Trimethylsilyl-substituted monomers have been shown to be more soluble and can polymerize more easily than non-TMS-substituted monomers, forming films that can be Figure 4-1. 3,4-Alkylenedioxythiophene-pyridine monomers fully characterized in this chapter.

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69 more homogeneous and provide better spectroelectrochemical results. 2 However, compound 6 did not polymerize as expected when a variety of techniques were used for deposition that included cyclic voltammetric, potentiostatic, and galvanostatic techniques. In addition to platinum, gold and glassy carbon electrodes also failed to give film formation upon oxidation using the above polymerization techniques. The electropolymerization of compound 4 , as shown in Figure 4-3, was carried out using the same monomer/electrolyte concentrations as monomer 1 . Compound 4 , though, Figure 4-2. 3,4-Alkylenedioxythiophene-pyridine monomers studied in this chapter. 2. Sotzing, G. A.; Reynolds, J. R.; Steel, P. J. Adv. Mater. 1997 , 9 , 795-798.

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70 Figure 4-3. Cyclic voltammetric deposition of poly( 1 ) (top) and poly( 4 ) (bottom) at a scan rate of 100 mV s -1 for 10 complete scans. The polymers were deposited on a 0.02 cm 2 platinum disk electrode from a 5 mM monomer/0.1 M tetran -butylammonium perchlorate/acetonitrile solution. Several drops of methylene chloride were added to assist in complete dissolution of the monomer in acetonitrile.

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71 behaves very differently than compound 1 . Scanning between 0.0 and +1.3 V gives an E p,m of +1.1 V as does compound 1 . The second scan leads to a slightly smaller current density at the peak potential, which is not unknown for the electrochemical polymerization of these types of monomers. 3 However, further scans lead to a positive shift of both the monomer oxidation, and the polymer oxidation peak potentials near +0.8 to +0.9 V. Current densities are much lower for all scans than those of compound 1 and decrease with multiple cycles as indicated by the arrow. Examination of the polymerization properties of two pyrido[3,4b ]pyrazine-based monomers is illustrated in Figure 4-4. The thiophene-based BTh-PyrPyr-Ph 2 has a very positive E p,m located at 1.4 V. This higher polymerization potential is expected as the terminal thiophene units are not as electron-rich as EDOT. Upon continued cycling, increases in current density are evident between +0.8 and +1.3 V due to polymer electrochemistry. In the region of the monomer oxidation, higher current densities are also seen due to the higher surface area as the conjugated polymer forms and a slight positive shift in monomer oxidation. As also seen in Figure 4-4, electropolymerization of monomer 2 leads to a lower E p,m than that of the thiophene derivative occuring at +1.1 V. Continued cycling gives higher current densities between +0.2 and +1.0 V corresponding to polymer deposition that increases upon further cycling. Between +1.0 V and +1.2 V the current density corresponding to monomer oxidation also increases as expected. 3. Groenendaal, L.; Jonas, F.; Freitag, D.; Pielartzik, H.; Reynolds, J. R. Adv. Mater. 2000 , 12 , 481-494 .

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72 Figure 4-4. Cyclic voltammetric deposition of poly( 9 ) (top) and poly( 2 ) (bottom) at a scan rate of 100 mV s -1 for 10 complete scans. The polymers were deposited on a 0.02 cm 2 platinum disk electrode from a 5 mM monomer/0.1 M tetran -butylammonium perchlorate/acetonitrile solution. Several drops of methylene chloride were added to assist in complete dissolution of the monomer in acetonitrile.

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73 As with the compound 6 , monomer 8 could not be efficiently electropolymerized using cyclic voltammetry, potentiostatic, or galvanostatic methods. As shown in Figure 45, when cyclic voltammetry is performed, current densities for monomer oxidation are approximately an order of magnitude less than the monomers shown in Figures 4-3 and 44. Upon repeated scanning, there is a small increase in current response is seen between +0.6 and +1.2 V. At the peak monomer oxidation potential of +1.3 V, the current density decreases on the second scan. Removal of the electrode from the monomer solution showed no visible polymer film on the surface. Figure 4-5. Attempted electrochemical polymerization of compound 7 at a scan rate of 100 mV s -1 for 10 complete scans. Polymerization was attempted on a 0.02 cm 2 platinum disk electrode from a 5 mM monomer/0.1 M tetran -butylammonium perchlorate/methylene chloride solution.

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74 Attempts to electropolymerize compound 5 gave similar results as with monomer 8 . No polymer was observed on the electrode surface using cyclic voltammetry, potentiostatic, or galvanostatic methods at platinum, gold, glassy carbon, and ITO electrodes. 4.3 Polymer Cyclic Voltammetry Characterization of the polymer films on platinum electrodes allows us to characterize the redox processes associated with these systems. As illustrated in Figure 46, cyclic voltammetric processes associated with poly( 1 ) include broad oxidation and reduction (to the neutral form) peaks centered at +1.1 V vs SCE. While the monomer’s E p,m is 200 mV higher than that of BEDOT-benzene (+0.9 V vs SCE), the resultant poly( 1 ) exhibits an E 1/2 that is 0.6 V more positive when compared to PBEDOT-benzene (+0.5 V). 4 This confirms the dominance of the terminal EDOT during polymerization, while the electron-accepting pyridine has a strong effect on the polymer’s redox properties. The film was cycled between +0.1 and +1.3 V twenty times to break-in the film, 5 and the last scan is shown for p-type doping. To examine the n-type doping properties, the polymer was scanned between +0.1 and -1.95 V twenty times. The last cycle was recorded, and the ntype doping electrochemistry is sharper and has a much more discernible E 1/2 at -1.6 V. This method allowed isolation of the two processes while experiments conducted by repeatedly cycling between pand n-type doped states led to the formation of pre-peaks that increased in intensity with each subsequent scan. [5], 6 These pre-peaks, which may result 4. Sotzing, G. A.; Reynolds, J. R.; Steel, P. J. Chem. Mater. 1996 , 8 , 882-889. 5. Zotti, G.; Schiavon, G.; Zecchin, S. Synth. Met. 1996 , 72 , 275-281.

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75 from trapped charge carriers, are sometimes misinterpreted as redox doping peaks if separate oxidation and reduction experiments are not performed. Poly( 4 ) was broken-in using the same procedure as that of poly( 1 ). The film was scanned from +0.55 to +1.6 V twenty times, and the last scan is shown in Figure 4-6. The polymer has a p-doping E 1/2 centered at +1.3 V which is about 200 mV more positive than 6. Thomas, C. T. Donor-Acceptor Methods for Band Gap Reduction in Conjugated Polymers: The Role of Electron Rich Donor Heterocycles. Ph. D. Dissertation, University of Florida, Gainesville, FL, 2002. Figure 4-6. Cyclic voltammetry of pand n-type doping of poly( 1 ), poly( 4 ), and poly( 2) in monomer-free 0.1 M tetran -butylammonium perchlorate/acetonitrile solution at 100 mV s -1 .

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76 poly( 1 ). As the electrochemistry of PEDOT and PProDOT-Me 2 are very similar to one another, this result was surprising for the pyridine polymers. This differing electrochemical behavior seems to indicate a possible structural difference between the two polymeric systems. The bulkier dimethyl-substituted dioxepine ring suggests a more open morphology for ion influx upon doping-dedoping, 7 but the relative electrochemistry between PEDOT and PProDOT-Me 2 are very similar. After n-doping break-in, poly( 4 ) behaved much like poly( 1 ) with an E 1/2 value of -1.6 V, though with a lower current density suggesting the reduction is centered on the acceptor unit. After breaking-in, poly( 2 ) also shown in Figure 4-6, has a broad oxidation process with no peak current upon oxidation. The relative shape of this process is similar to that of PBEDOT-Pyr, but with an onset shifted about 100 mV more positive. This slight shift is likely a consequence of the stronger pyrido[3,4b ]pyrazine acceptor perturbing the valence band levels of the D-A polymer. Due to the increased acceptor strength of the PyrPyr-Ph 2 unit, two reduction processes occur centered at -1.0 and -1.6 V. The increased acceptor strength allows for the insertion of a second electron per polymer repeat unit at the same potential as poly( 1 ). It is interesting to note that the reduction potential of poly( 2 ) is roughly 100 to 200 mV more positive than those of the thiophene-based pyrido[3,47. (a) Kumar, A.; Welsh, D. M.; Morvant, M. C.; Piroux, F.; Abboud, K. A.; Reynolds, J. R. Chem. Mater. 1998 , 10 , 896-902. (b) Welsh, D. M.; Kumar, A.; Meijer, E. W.; Reynolds, J. R. Adv. Mater. 1999 , 11 , 1379-1382.

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77 b ]pyrazine polymers 8 and pyrido[3,4b ]pyrazine-vinylene copolymers, 9 demonstrating the effect the donor has on the conduction band in relative energy space. A closer examination of the reduction behavior of the pyrido[3,4b ]pyrazine family is shown in Figure 4-7. Poly( 2 ), as discussed in the preceding paragraph, has a reduction centered at -1.0 V. In comparison, the solution reduction electrochemistry of PyrPyr-Ph 2 , monomer 2 , and monomer 5 in acetonitrile behaves similar to all three systems having E 1/ 2 values of -1.0 V. It has previously been demonstrated that there is a direct correlation between reduction E 1/2 values and the LUMO level of the system under study. 10 Examination of the reductive electrochemistry of the acceptor molecules serves as an easy method to predict LUMO values for the polymers under investigation. One of the most puzzling problems associated with reduction electrochemistry of conjugated polymers is the lack of understanding of the n-doped state. One method of better understanding doping induced changes is to examine electrolyte behavior. 11 Four electrolytes were chosen to characterize these systems: TBAP, TEAP, NaP, and LiP. As can be seen in Figure 4-8, the reproducible cyclic voltammetry behavior upon oxidation for each polymer are well-behaved for each electrolyte system used. Onsets and associated E 1/ 2 values are consistent with the behavior of other p-type doping polymers, including 8. Lee, B.-L.; Yamamoto, T. Macromolecules 1999 , 32 , 1375-1382. 9. Jonforsen, M.; Johansson, T.; Ingans, O.; Andersson, M. R. Macromolecules 2002 , 35 , 1638-1643. 10. (a) Streitwieser, A., Jr. Molecular Orbital Theory for Organic Chemists ; Wiley: New York, NY, 1961. (b) Streitwieser, A.; Schwager, I. J. Phys. Chem. 1962 , 66 , 2316-2320. 11. (a) Aubert, P.-H.; Groenendaal, L.; Louwet, F.; Lutsen, L.; Vanderzande, D.; Zotti, G. Synth. Met. 2002 , 126 , 193-198. (b) Tourillion, G.; Garnier, F. J. Phys. Chem. 1983 , 87 , 2289-2292.

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78 PEDOT. The relative onsets and E 1/2 values are expected to differ slightly for each electrolyte studied due to the hard-soft behavior of each electrolyte cation-anion pair. [11] As shown in Figure 4-8, poly( 1 ) has an E 1/2 value of +1.1 V for both TBAP and TEAP. Replacement of the electrolyte solution with NaP provides for an E 1/2 value of +0.9 V. LiP, the hardest cation-anion electrolyte pair, exhibits the largest current densities and an E 1/2 centered at +0.9 V. Figure 4-8 also shows the electrochromic color changes evident to the two polymers. Details on these color changes are discussed in detail in section 4-6. Figure 4-7. Cyclic voltammetry of the n-type doping of poly( 2 ). The solution reduction electrochemistry of PyrPyr-Ph 2 , monomer 1 , and monomer 5 are also shown. All solutions were 5 mM analyte in 0.1 M tetran -butylammonium perchlorate/acetonitrile. The experiment was performed on a 0.02 cm 2 platinum disk electrode at a 100 mV s -1 scan rate.

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79 Figure 4-8. Cyclic voltammetry of poly( 1 ) (top) and poly( 2 ) (bottom) in four electrolyte systems: tetran -butylammonium perchlorate, tetran -ethylammonium perchlorate, sodium perchlorate, and lithium perchlorate. The experiment was performed at 100 mV s -1 in monomer-free electrolyte solution (0.1 M perchlorate salt/acetonitrile). The colors of the polymers at each distinct redox state are inset.

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80 Of the four electrolyte systems upon reduction though, only TBAP and TEAP exhibit well-behaved redox behavior at negative potentials. Both TBAP and TEAP give sharp reductions centered at -1.6 V. TBAP has the highest current densities of all four electrolyte systems. NaP does display a visible current density, but the E 1/2 values could not be determined as a consequence of the ever increasing current density. The current density associated with LiP is indiscernible from background current. These potential shifts provide the first suggestion that polymer-ion interactions are vital to describing ntype doping processes. As seen in Figure 4-8, poly( 2 ) has current densities associated with oxidation that are of the same relative magnitude for all of the electrolyte systems. The increase in acceptor strength only slightly affects the E 1/2 values upon oxidation (valence band level). None of the systems have an easily discernible E 1/2 ; rather, the current densities increase continually. As with poly( 1 ), poly( 2 ) displays visible current densities with TBA + and TEA + upon electrochemical reduction. Due to the stronger acceptor content of this polymer, two reductions attributed to n-type doping are seen. Poly( 2 ) in the TBA + system displays an E 1/2 at -1.1 V for the first reduction. The second reduction matches that of TBA + doping of poly( 1 ) with an E 1/2 located at -1.7 V. The smaller TEA + cation also has an E 1/2 value of -1.1 V for the first reduction. The second reduction however occurs at a slightly more positive E 1/2 value at -1.6 V. Of the alkali cations used in this study, only Na + displayed a current response in the potential range examined. The E 1/2 values associated with the two reductions also behaved as those of the bulkier cations with values of -1.2 and -1.6 V

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81 As illustrated in Figure 4-9, the donor-acceptor nature of these structures lead to stabilized charge separated resonance forms for the undoped monomers (and thus polymers) that hint at potential stabilized reduction sites. Compound 1 has only one resonance stabilized state indicating the ability of the single nitrogen on the pyridine can only stabilize one negative charge. Of the three resonance states associated with compound 2 , two are localized on the pyrazine ring. The ability of this ring system to accommodate more electron density than the pyridine ring 12 implies that the first reduction seen in this system is expected to be stabilized here. Since the pyridine ring only stabilizes one electron, the second reduction displayed is expected to appear here. This is verified by the CV data as the second reduction of poly( 2 ) very closely matches that of poly( 1 ). 12. de Leeuw, D. M.; Simenon, M. M. J.; Brown, A. R.; Einerhand, R. E. F. Synth. Met . 1997 , 87 , 53-59. Figure 4-9. Resonance behavior and potential charge stabilized reduction sites of poly( 1 ) and poly( 2 ).

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82 4.4 Polymer Differential-Pulse Voltammetry Electrolyte effects were also studied using differential-pulse voltammetry (DPV). DPV offers better sensitivities than CV and leads to both sharper redox peaks and peak onsets due to current responses that only occur near the E 0` region. 13 The peak shapes seen in DPV also allude to the redox behavior of the systems. True reversible systems exhibit sharper, more well-defined peaks; while quasi-reversible and irreversible systems give broad peaks with lower current densities than reversible systems. To date, very few studies have examined the fundamental behavior of conjugated polymers using DPV; rather, most efforts have been focused on sensor and release applications. 14 For poly( 1 ), shown in Figure 4-10, the oxidation processes have sharper onsets than those associated with cyclic voltammetry, yet no peak shape is seen. This observation indicates a quasi-reversible or irreversible process. Of these four electrolytes, only the soft electrolytes (TBAP and TEAP) show an appreciable current response upon reduction. Both NaP and LiP have current densities that are indiscernible from background current. Poly( 2 ) behaves similarly to poly( 1 ) upon oxidation. All four electrolyte systems have sharp onsets and broad current responses indicative of quasi-reversible or irreversible processes. Relative current densities and onsets for poly( 2 ) match those of poly( 1 ) quite 13. Richardson, D. E.; Taube, H. Inorg. Chem. 1981 , 20 , 1278-1285. 14. (a) Ciszewski, A.; Milczarek, G. Anal. Chem. 1999 , 71 , 1055-1061. (b) Diab, N.; Schuhmann, W. Electrochim. Acta 2001 , 13 , 860-867. (c) Ekinci, E.; Erdogdu, G.; Karagozler, A. E. J. Appl. Poly. Sci. 2000 , 79 , 327-332. (d) Fabre, B.; Burlet, S.; Cespuglio, R.; Bidan, G. J. Electroanal. Chem. 1997 , 426 , 75-83. (e) Jin, S.; Cong, S.; Zue, G.; Xiong, H.; Mansdorf, B.; Cheng, S. Z. D. Adv. Mater. 2002 , 14 , 1492-1496. (f) Komura, T.; Kijima, K.; Yamaguchi, T.; Takahashi, K. J. Electroanal. Chem. 2000 , 486 , 166-174. (g) Nishiumi, T.; Higuchi, M.; Yamamoto, K. Electrochemistry 2002 , 70, 668-670. (h) Reynes, O.; Gulon, T.; Moutet, J.-C.; Royal, G.; Saint-Aman, E. J. Organomet. Chem. 2002 , 656 , 116-119.

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83 Figure 4-10. Differential-pulse voltammetry of poly( 1 ) (top) and poly( 2 ) (bottom) in tetran -butylammonium perchlorate, tetran -ethylammonium perchlorate, sodium perchlorate, and lithium perchlorate (0.1 M perchlorate salt/acetonitrile) electrolyte solutions. The experiment was performed with a step time of 0.0167 sec, a step size of 2 mV, amplitude 1 0 mV with four data points collected, and amplitude 2 of 100 mV with one data point collected.

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84 well indicating that the bi-EDOT donor is not significantly affected by increasing the acceptor strength. Upon reduction, one redox process for poly( 1 ) and two redox processes for poly( 2 ) are seen, as in the CV experiment. TBAP yields an E 1/2 of -1.0 V. TEAP has E 1/2 values of -1.0 V for the first reduction and -1.5 V for the second reductions. Of the metal salts, only NaP has E 1/2 values which are located at -1.1 and -1.5 V. NaP only exhibits a color change from the neutral to first n-doped state but no second color change to the second ndope state. With LiP, however, no color change or redox behavior is observed even when the experiment is conducted out to -1.9 V. 4.5 In-situ Conductivity In-situ conductance experiments were performed on poly( 1 ) according to the steady-state method of Wrighton and others 15 and further reinforce the CV and DPV results. Measurements of the conductance of thin polymer films on interdigitated microelectrodes show onsets of the doping processes consistent with that from cyclic voltammetry (Figure 4-11). p-Doping for both poly( 1 ) and poly( 2 ) show sharp onsets at +0.25 V. In this experiment, both poly( 1 ) and poly( 2 ) show very large conductance increases that remain high as the potential is stepped positively as expected for highly electronically conducting polymers. The conductance due to n-doping of poly( 1 ) at -1.8 V is about 30 times less than that observed for p-doping. To the best of our knowledge, this is the smallest p-type/n-type conductance ratio reported for a polyheterocycle of this type. 15. (a) Kittlesen, G. P.; White, H. S.; Wrighton, M. S. J. Am. Chem. Soc. 1984 , 106 , 73897396. (b) Paul, E. W.; Ricco, A. J.; Wrighton, M. S. J. Phys. Chem . 1985 , 89 , 14411447. (c) Schiavon, G.; Sitron, S.; Zotti, G. Synth. Met. 1989 , 32 , 209-217. (d) Thackeray, J. W.; White, H. S.; Wrighton, M. S. J. Phys. Chem. 1985 , 89 , 5133-5140.

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85 Poly( 1 ) has an onset for n-doping at -1.5 V. Peak conductance occurs at -1.85 V with a shoulder at -1.65 V. As stated earlier, poly( 2 ) can accept two electrons per repeat unit, and this is seen as two peaks centered at -1.0 and -1.5 V. Given the conductance profile in the reduction region, it is likely that a combination of both a redox transport mechanism 16 and n-doping is occurring, and formation of a highly delocalized anionic state is unlikely as no capacitive effect is seen. Decreased mobility, or pinning, of the anionic charge can explain this lower conductance on reduction. 17 Of the electrolyte systems examined, only TBAP and TEAP had an appreciable increase in conductance upon reduction with values of 0.18 mS and 0.31 mS, respectively. Onset of the conductance increase occurred at -1.6 V and peaked at -1.8 before decreasing for TEAP. TBAP had an onset of -1.5 V with a conductance maximum at -1.9 V. Reduction with NaP did lead to a noticeable conductance increase with an onset at -1.6 V, but the peak shifted more negative to almost -1.9 V and only had a conductance of 0.03 mS. LiP had a response undetectable from the background. The results from examination of poly( 2 ) shown in Figure 4-12 are more startling. NaP had the largest conductance of the electrolyte systems with an onset at -0.8 V and a peak conductance of 0.25 mS at -1.1 V. However, upon further reduction only a small peak is seen at -1.3 V. TEAP and TBAP had the same onset at -0.8 V as NaP did, but TEAP had a smaller relative conductance of 0.07 mS with a larger peak at -0.9 V. Associated with the 16. (a) Long, J. W.; Kim, I. K.; Murray, R. W. J. Am. Chem. Soc. 1997 , 119 , 1151011515. (b) Williams, M. E.; Crooker, J. C.; Pyati, R.; Lyons, L. J.; Murray, R. W. J. Am. Chem. Soc. 1997 , 119 , 10249-10250. (c) Williams, M. E.; Masui, H.; Long, J. W.; Malik, J.; Murray, R. W. J. Am. Chem. Soc. 1997 , 119 , 1997-2005. 17. (a) Reynolds, J. R.; Schlenoff, J. B.; Chien, J. C. W. J. Electrochem. Soc. 1985 , 132 , 1131-1135. (b) Zotti, G.; Schiavon, G.; Zecchin, S. Synth. Met. 1996 , 72 , 275-281.

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86 second color change is another peak centered at -1.4 V with an onset of -1.3 V and maximum conductance of 0.1 mS. TBAP had a small conductance of 0.03 mS for the first peak and 0.056 mS for the second peak. LiP displayed a rather small conductance of 0.01 mS at -1.2 V. TBAP and TEAP exhibited the expected color changes upon reduction. Both NaP unexpectedly exhibited color changes associated with the first redox peak, but there were none with the second indicating that n-type doping occurs at the first peak and only redox-type conductivity is seen upon further reduction. This observation further illustrates that n-type doping can not be discerned by simple voltammetry as illustrated in Figures 46, 4-7, 4-8, and 4-10, but rather, more detailed experiments are need before such conclusions are made. Figure 4-11. In-situ conductance of poly( 1 ) ( red ) and poly( 2 ) ( blue ) in tetran butylammonium perchlorate (0.1 M perchlorate salt/acetonitrile) electrolyte solutions. The experiment was performed on an interdigitated microelectrode with 100 bands 5 m m bands spaced 5 m m apart. Note two different conductance scales for pand n-type doping

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87 Figure 4-12. In-situ conductance of the n-type doping region of poly( 1 ) (top) and poly( 2 ) (bottom) in tetran -butylammonium perchlorate, tetran -ethylammonium perchlorate, sodium perchlorate, and lithium perchlorate (0.1 M perchlorate salt/acetonitrile) electrolyte solutions. The experiment was performed on an interdigitated microelectrode with 100 bands 5 m m bands spaced 5 m m apart.

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88 4.6 Polymer Spectroelectrochemistry As discussed in the previous sections, only monomers 1 , 2 and 4 could be easily electropolymerized. For this reason, a focussed study of the optical properties of these systems was undertaken. The polymer films were also electrochemically polymerized on ITO in order to carry out optical studies using a constant potential method from acetonitrile to charge densities of 25 mC cm -2 (approximately 300 nm in thickness). The neutral UV-Vis-NIR spectra of poly( 1 ), poly( 2 ), poly( 4 ), and poly( 9 ) are shown in Figure 4-13. Poly( 1 ) and poly( 4 ) have band gaps of 1.9 eV with poly( 1 ) exhibiting a l max value of 475 nm (2.6 eV). Incorporation of the ProDOT-Me 2 unit, to give poly( 4 ), causes a 10 nm red shift in l max for that polymer to 485 nm (2.6 eV) with a more narrow band width. Poly( 9 ) has a band gap of 1.6 eV and a l max value of 570 nm (2.2 eV). Poly( 2 ), due to the higher HOMO level of the bi-EDOT unit relative to bi-thiophene, has the lowest band gap of all the polymers investigated of 1.2 eV and two l max values of 425 nm (2.9 eV) and 750 nm (1.7 eV). Although poly(1) and poly(4) have identical band gaps, the differing widths of their absorption profile result in different colors for the neutral polymers. Poly( 1 ) is a bright red, while poly( 4 ) is a lighter red, almost pink color. Poly( 9 ) is a lavender color when neutral, and poly( 2 ) is lime green. A more complete discussion of color and color changes upon doping is offered in Section 4-7. When poly( 1 ) is held between -0.65 V and 0.0 V in a spectroelectrochemical experiment in an argon purged cuvette on the bench top, the neutral film is a deep red color as described in Section 4-7. This optical state is similar to polythiophene and its alkyl substituted analogues, and, as expected, the band gap lies between the values observed for PEDOT (1.6 eV) and polypyridine (2.7 eV) shown in Figure 4-14. 18 Incremental oxidation

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89 leads to depletion of the p p * region with growth upon intermediate doping of a peak at 1.6 eV and absorption below 1 eV. Upon more complete doping, the intermediate transition decreases in magnitude while the 0.9 eV transition increases. Upon complete doping the film becomes a navy blue. These spectral results show polythiophene like behavior. 18. Schiavon, G.; Comisso, N.; Toniolo, R.; Bontempelli, G. Anal. Chim. Acta 1995 , 305 , 212. Figure 4-13. UV-Vis-NIR spectrum of neutral poly( 1 ), poly( 2 ), poly( 4 ), and poly( 9 ) on an ITO-coated glass slide. All films were deposited potentiostatically from a 5 mM monomer/0.1 M tetran -butylammonium perchlorate/acetonitrile solution until 25 mC cm 2 of charge density had passed.

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90 Hydrazine neutralization does not fully remove the NIR absorption and may be due to the background absorption in the low wavelength region. Poly( 4 ) has an identical bandgap of 1.9 eV along with a similar spectroelectrochemical response as that of poly( 1 ) as shown in Figure 4-14. The relative bandwidth of the p p * transition is narrower leading to the different colors exhibited for each redox state. The neutral polymer is red-orange in color which changes to a royal purple upon oxidation. Reduction gives a pale blue-gray polymer that is almost completely transmissive. Upon step-wise oxidation, the p p * transition becomes depleted with a peak growing in at 1.0 eV upon full oxidation. Spectroelectrochemical studies of poly( 2 ) reveal an onset at 1.2 eV for the neutral polymer as presented in Figure 4-15 with the polymer held at -0.15 V. The first peak at an l max of 1.65 eV (750 nm) is attributed to the p p * transition (E 1u (x)) common in conjugated polymers and is accompanied by a second strong absorption at an l max of 2.9 eV (424 nm). This second absorption is due to polarization perpindicular to the polymer chain (E 1u (y)). 19 Upon incremental stepping of the potential (100 mV intervals) from -0.15 V to +1.45 V, both transitions observed in the neutral polymer decrease in intensity. At intermediate potentials, a peak evolves at 1.45 eV (850 nm) attributable to the charge carriers that are formed, which is subsequently overwhelmed by the strong NIR absorption upon further doping. At fully p-doped potentials, an absorption maximum centered at 1.05 19. (a) Gartstein, Y. N.; Rice, M. J.; Conwell, E. M. Phys. Rev. B 1995 , 51 , 5546-5549. (b) Gartstein, Y. N.; Rice, M. J.; Conwell, E. M. Phys. Rev. B 1995 , 52 , 1683-1691. (c) Kim, S.; Jackiw, J.; Robinson, E.; Schanze, K. S.; Reynolds, J. R.; Baur, J.; Rubner, M. F.; Boils, D. Macromolecules 1998 , 31 , 964-974.

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91 Figure 4-14. Spectroelectrochemistry of a film of poly( 1 )(top) on an ITO-coated glass slide at applied potentials of (a) -0.65, (b) -0.25, (c) +0.25, (d) +0.30, (e) +0.35, (f) +0.40, (g) +0.45, (h) +0.50, (j) +0.55, (k) +0.60, (l) +0.65, (m) +0.70, (n) +0.75, (o) +0.80, (p) +0.85, (q) +0.90, (r) +0.95, (s) +1.00, (t) +1.05, (u) +1.10, (v) +1.15, and (w) +1.20 V vs SCE. Spectroelectrochemistry of a film of poly( 4 ) (bottom) on an ITO-coated glass slide at applied potentials of (a) +0.1, (b) +0.6, (c) +0.7, (d) +0.8, (e) +0.9, (f) +1.0, (g) +1.1, (h) +1.2, and (i) +1.3 V vs SCE.

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92 eV (1175 nm) provides the main spectral feature with strong tailing into the visible region consistent with a highly doped state. As a result of thiophene being less electron rich than EDOT, poly( 9 ) has a band gap of 1.6 eV, 0.2 eV higher than poly( 2 ) as illustrated in Figure 4-15. Two l max values are present at 570 nm (2.2 eV) and 355 nm (3.5 eV), analogous to poly( 2 ). These two absorptions also correspond to polarization along the polymer chain’s axis (low energy) and cross-axis polarization (high energy). Upon step-wise oxidation the p p * transition decreases with a peak at 1.0 eV that grows upon full oxidation. Above 1.1 V, the polymer begins to degrade as the film becomes over-oxidized. This illustrates the benefit of the biEDOT linkage relative to the bi-Th linkage, which is substantially more difficult to oxidize. Due to the insolubility of monomer 7 in acetonitrile, film formation was attempted in a saturated methylene chloride solution. After prolonged potentiostatic electropolymerization, a film was able to be grown on an ITO-coated glass slide; however, the polymer film was inhomogeneous and poorly coated the glass substrate. The onset of the p p * transition is near 1.4 eV, and it’s behavior upon incremental doping behaves much like that of poly( 2 ). In this case only incomplete doping is achieved before the film becomes over-oxidized and degrades. The spectrum was also much noiser than that of the other polymers examined because an older instrument was used. In order to characterize the reduction of these donor-acceptor-donor polymers, spectroelectrochemical experiments were performed in an argon-filled drybox with a fiber optic CCD/InGaAs detector. As illustrated in Figure 4-17, the p-type doping of poly( 1 ) has a neutral l max near 510 nm (2.4 eV). These results are comparable to those in Figure 4-14. Preparation of the films in an argon-filled drybox rather then on the benchtop under

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93 Figure 4-15. Spectroelectrochemistry of a film of poly( 2 ) (top) on an ITO-coated glass slide at applied potentials of (a) -0.65, (b) -0.25, (c) +0.25, (d) +0.30, (e) +0.35, (f) +0.40, (g) +0.45, (h) +0.50, (i) +0.60, (j) +0.65, (k) +0.70, (l) +0.75, (m) +0.80, (n) +0.85, (o) +0.90, (p) +0.95, (q) +1.00, (r) +1.05, (s) +1.10, (t) +1.15, and (u) +1.20 V vs SCE. Spectroelectrochemistry of a poly( 9 ) (bottom) film on an ITO-coated glass slide at applied potentials of (a) -0.5, (b) -0.4, (c) -0.3, (d) -0.2, (e) -0.1, (f) 0.0, (g) +0.1, (h) +0.2, (i) +0.3, (j) +0.4, (k) +0.5, (l) +0.6, (m) +0.7, (n) +0.8, (o) +0.9, (p) +1.0, and (q) +1.1 V vs SCE.

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94 ambient conditions leads to a 35 nm red shift in l max relative to films prepared outside of the drybox due most likely to a lower defect density along the polymeric backbone. Upon oxidation by stepping potentials in 0.1 V increments from -0.9 to 0.0 V leads to no change in optical properties. At +0.1 V, the p p * transition decreases as an intermediate charge carrier peak forms near 2.0 eV. More complete oxidation occurs at +1.4 V with a decrease in the polaron absorption and growth of a bipolaron absorption band at energies greater than 1.4 eV. These spectral features are qualitatively indentical to Figure 4-14 demonstrating the validity of the fiber optic measurement.. Figure 4-16. Spectroelectrochemistry of a film of poly( 7 ) on an ITO-coated glass slide at various applied potentials.

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95 Figure 4-17. Poly( 1 ) spectroelectrochemistry on an ITO-coated glass slide in monomerfree 0.1 M tetran -butylammonium perchlorate/acetonitrile electrolyte solution. p-Type doping (top) applied potentials are (a) -0.9, (b) +0.1, (c) +0.2, (d) +0.30, (e) +0.4, (f) +0.5, (g) +0.6, (h) +0.7, (i) +0.8, (j) +0.9, (k) +1.0, (l) +1.1, (m) +1.2, (n) +1.3, and (o) +1.4 V vs SCE. n-Type doping (bottom) applied potentials are (a) -0.9, (b) -1.0, (c) -1.1, (d) -1.2, (e) -1.3, (f) -1.4, (g) -1.5, (h) -1.55, (i) -1.6, (j) -1.65, (k) -1.7, (l) -1.75, (m) -1.8, (n) -1.85, and (o) -1.9 V vs SCE.

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96 Using the fiber opticspectrophotometer in the dry box, examination of n-type doping in TBA + electrolyte, shown in Figure 4-27, a similar spectral signature to p-doping occurs, though the nature of the carriers are vastly different. The neutral p p * transition has a l max of 510 nm. As the potential is stepped negative from -1.10 V to -1.90 V, the visible transition decreases steadily until -1.70 V is reached at which point the p p * transition decreases rapidly and achieves complete depletion with formation of only an intermediate charge carrier band centered at 1.75 eV. One possible explanation for this is the noticably sharper reduction cyclic and differential pulse voltammetry compared in Figures 4-8 and 4-10. Application of more negative potentials leads to a decrease in the low energy absorptions accounted by the degradation of the polymer film. The overall absorbance is slightly lower in intensity and red shifted relative to the oxidized state (0.4 AU vs 0.6 AU) leading to the more transmissive sky blue color. The NIR absorbance is maximum at -1.8 V. Further applied potentials lead to a decrease in absorption as the film degrades due to over-reduction. Changing the electrolyte to TEAP allows us to observe similar results to those of ptype doping of poly( 1 ) when TBAP is used. As seen in Figure 4-18, l max for the neutral polymer is located at 510 nm. Application of potentials to cause oxidation (E > +0.1 V) cause depletion of the p p * transition, and an intermediate charge carrier peak grows in centered near 1.8 eV. NIR absorption on the other hand behaves similar to TBAP, but with higher absorbance values. It should be noted that the Vis and NIR results in a single figure originate from two different films. Oxidation causes a charge carrier peak to grow in as potentials higher than +0.4 V are applied to the polymer film. Upon complete oxidative doping, a sharp peak centered near 1.0 eV is visible.

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97 Figure 4-18. Poly( 1 ) spectroelectrochemistry on an ITO-coated glass slide in monomerfree 0.1 M tetran -ethylammonium perchlorate/acetonitrile electrolyte solution. p-Type doping (top) applied potentials are (a) -0.9, (b) +0.1, (c) +0.2, (d) +0.30, (e) +0.4, (f) +0.5, (g) +0.6, (h) +0.7, (i) +0.8, (j) +0.9, (k) +1.0, (l) +1.1, (m) +1.2, (n) +1.3, and (o) +1.4 V vs SCE. n-Type doping (bottom) applied potentials are (a) -1.0, (b) -1.1, (c) -1.2, (d) -1.3, (e) -1.5, (f) -1.5, (g) -1.6, (h) -1.7, (i) -1.8, and (j) -1.9 V vs SCE.

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98 When reduction potentials are applied to poly( 1 ) in TEA + , the neutral absorption decreases steadily until at -1.80 V a drastic change occurs as the absorption associated with the p p * transition is completely bleached (Figure 4-18). Most likely due to the sharper reduction compared to oxidation. An intermediate charge carrier band is present at 1.8 eV. Upon complete doping, a broader absorbance forms at 0.9 eV. This may be due to easier insertion of the smaller TEA + cation into the film suggesting a higher degree of doping. At potentials more negative than -1.8 V, the NIR absorption begins to decrease indication degradation of the film. Spectroelectrochemistry using NaP is shown in Figure 4-19. The p p * transition is located at 510 nm. Upon incremental oxidation, l max and the absoroption are red shifted as polaron absorption bands increase between 1.5 and 2.0 eV. Full oxidation leads to a bipolaron absorption maximum at 1.0 eV as expected for a polymer that attains high doping levels. Reduction using the Na + electrolyte solution is much different than when TBA + and TEA + are used as shown in Figure 4-19. The absorption associated with the p p * transition decreases and is highly bleached, but no intermediate charge carrier formation is observed. This decrease is most likely due to polymer decomposition as highly negative potentials are applied. In the NIR region, the absorption increases slightly, but is not due to bipolaron charge carrier formation indicating no doping process. Spectroelectrochemistry with LiP as the electrolyte is shown in Figure 4-20. Its pdoping behavior is identical to that of NaP as expected since perchlorate is the dominant dopant. However upon application of reductive potentials (black trace) no absorption

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99 Figure 4-19. Poly( 1 ) spectroelectrochemistry on an ITO-coated glass slide in monomerfree 0.1 M sodium perchlorate/acetonitrile electrolyte solution. p-Type doping (top) applied potentials are (a) -0.9, (b) -0.4, (c) -0.2, (d) -0.1, (e) 0.0, (f) +0.1, (g) +0.5, (h) +0.6, (i) +0.7, (j) +0.8, (k) +0.9, (l) +1.0, (m) +1.1, (n) +1.2, (o) +1.3, and (p) +1.4 V vs SCE. nType doping (bottom) applied potentials are (a) -0.9, (b) -1.5, (c) -1.6, (d) -1.7, (e) -1.8, and (f) -1.9 V vs SCE.

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100 change is seen in the NIR region, and the decrease in visible absorption is attributed to degradion of the polymer due to over-reduction. Spectroelectrochemical examination of electrolyte effects of TBAP with poly( 2 ) are shown in Figure 4-21. The neutral absorption gives peaks in the visible region located at 750 nm and near 400 nm. Step-wise oxidation causes decreases in height of both peaks. Upon complete oxidation, a NIR dominant peak occurs that tails into the visible region Figure 4-20. Poly( 1 ) spectroelectrochemistry on an ITO-coated glass slide in monomerfree 0.1 M lithium perchlorate/acetonitrile electrolyte solution. Applied potentials are (a) 1.0, (b) +0.2, (c) +0.3, (d) +0.4, (e) +0.5, (f) +0.6, (g) +0.7, (h) +0.8, (i) +0.9, (j) +1.0, (k) +1.1, (l) +1.2, (m) +1.3, and (n) +1.4 V vs SCE.

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101 resulting in the gray-green color of the oxidized film. Examination of the NIR region using TBAP as the electrolyte show little absorption of the neutral polymer. Upon application of a positive potential, a peak grows rapidly near 900 nm, but upon higher doping levels absorption becomes broad across the entire NIR region. Upon n-type doping of poly( 2 ) in TBAP, the 750 nm peak decreases in height as doping occurs to give tailing from the blue visible region into the NIR as seen in Figure 421. The high energy peak near 400 nm grows in height to give a burgundy red film color upon reduction at -1.1 V and a dark gray upon complete reduction of the film at -1.9 V. Reduction, on the other hand, shows little change in the NIR region. This indicates that the oxidation and reduction processes are different, hence the different colors associated with each redox state. By changing the electrolyte system to TEAP, poly( 2 ) gives similar results upon ptype doping. The high energy peak at 435 nm disappears upon oxidation demonstrated in Figure 4-22. A peak centered above 850 nm grows in as the polymer is oxidized step-wise. Examination of the NIR region reveals similar results to the TBAP experiment. The neutral polymer displays little absorption in this region. As step-wise oxidative potentials are applied, an intermediate charge carrier band begins to grow near 900 nm. As further positive potentials are applied, another charge carrier band grows in until broad absorption occurs across the entire NIR region. Upon n-type doping, the results are more striking. Little change is seen for the peak at 400 nm. However, upon reduction, the p p * transition decreases and a new peak grows in at 545 nm. In contrast, no change occurs in the NIR upon reduction when potentials up to -1.9 V are applied indicating little doping occuring.

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102 Figure 4-21. Poly( 2 ) spectroelectrochemistry on an ITO-coated glass slide in monomerfree 0.1 M tetran -butylammonium perchlorate/acetonitrile electrolyte solution. p-Type doping (top) applied potentials are (a) -0.6, (b) -0.4, (c) -0.2, (d) 0.0, (e) +0.2, (f) +0.4, (g) +0.6, (h) +0.8, (i) +1.0, (j) +1.2, and (k) +1.4 V vs SCE. n-Type doping (bottom) applied potentials are (a) -0.5, (b) -0.7, (c) -0.9, (d) -1.1, (e) -1.3, (f) -1.5, (g) -1.7, and (h) -1.9 V vs SCE.

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103 Figure 4-22. Poly( 2 ) spectroelectrochemistry on an ITO-coated glass slide in monomerfree 0.1 M tetran -ethylammonium perchlorate/acetonitrile electrolyte solution. p-Type doping (top) applied potentials are (a) -0.6, (b) -0.4, (c) -0.2, (d) 0.0, (e) +0.2, (f) +0.4, (g) +0.6, (h) +0.8, (i) +1.0, (j) +1.2, and (k) +1.4 V vs SCE. n-Type doping (bottom) applied potentials are (a) -0.6, (b) -0.7, (c) -0.8, (d) -0.9, (e) -1.0, (f) -1.1, (g) -1.2, (h) -1.3, (i) -1.4, (j) -1.5, (k) -1.6, (l) -1.7, (m) -1.8, and (n) -1.9 V vs SCE.

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104 Substitution of the n -alkylammonium perchlorates with NaP leads to little change in the p-type doping spectroelectrochemistry as shown in Figure 4-23. However, if reduction potentials are applied, dramatic changes occur relative to p-type doping. All absorptions above 2.25 eV are bleached as potentials are stepped from -0.6 to -1.9 V. The high energy absorption located at 2.75 eV increases in size and becomes slightly red shifted to 2.6 eV. The green neutral color becomes bright orange upon complete reduction. Lack of charge carrier formation indicates that doping does not occur even though a color change is seen. Spectroelectrochemistry performed with LiP is identical in the p-type doping region as the previous electrolytes examined as seen in Figure 4-24. Once again, reductive spectroelectrochemistry is much different than p-type doping. All absorptions above 2.2 eV become completely bleached, and no charge carrier formation is shown. The absorption peak seen at 2.7 eV increases in size and is red shifted to 2.6 eV. No doping process occurs as the film changes from a lime green to a bright orange color. 4.7 Polymer Colorimetry The previous section detailed spectroscopic analysis of these conjugated polymer systems; however, a fundamentally different way to examine these systems is to use colorimetry to precisely define the color of the polymer films as sensed by the human eye mathematically. As described in chapter 2, the method of choice for these experiments is the CIE 1931 systems and this method has been applied to a number of electrochromic polymers studied by the Reynolds group. 20 20. Thompson, B. C.; Schottland, P.; Zong, K.; Reynolds, J. R. Chem. Mater. 2000 , 12 , 1563-1571

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105 Figure 4-23. Poly( 2 ) spectroelectrochemistry on an ITO-coated glass slide in monomerfree 0.1 M sodium perchlorate/acetonitrile electrolyte solution. p-Type doping (top) applied potentials are (a) -0.6, (b) -0.4, (c) -0.2, (d) 0.0, (e) +0.2, (f) +0.4, (g) +0.6, (h) +0.8, (i) +1.0, (j) +1.2, and (k) +1.4 V vs SCE. n-Type doping (bottom) applied potentials are (a) -0.6, (b) -0.7, (c) -0.8, (d) -0.9, (e) -1.0, (f) -1.1, (g) -1.2, (h) -1.3, (i) -1.4, (j) -1.5, (k) -1.6, (l) -1.7, (m) -1.8, and (n) -1.9 V vs SCE.

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106 Figure 4-24. Poly( 2 ) spectroelectrochemistry on an ITO-coated glass slide in monomerfree 0.1 M litium perchlorate/acetonitrile electrolyte solution. p-Type doping (top) applied potentials are (a) -0.6, (b) -0.4, (c) -0.2, (d) 0.0, (e) +0.2, (f) +0.4, (g) +0.6, (h) +0.8, (i) +1.0, (j) +1.2, and (k) +1.4 V vs SCE. n-Type doping (bottom) applied potentials are (a) 0.6, (b) -0.7, (c) -0.8, (d) -0.9, (e) -1.0, (f) -1.1, (g) -1.2, (h) -1.3, (i) -1.4, (j) -1.5, (k) -1.6, (l) -1.7, (m) -1.8, and (n) -1.9 V vs SCE.

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107 Neutral poly( 1 ) is a bright red color, as shown by its dominant wavelength of 610 nm and location farthest from the illumination source, also called the white point, indicating the color to be the most saturated (Figure 4-25). Upon incremental doping by application of oxidative potentials, poly( 1 ) changes to a blue-purple color ( l d of 485 nm) located near the illumination source, explaining it’s less intensely colored state. Increase of acceptor strength by thebaddition of the pyrido[3,4b ]pyrazine group to form poly( 2 ) leads to a neutral lime green color with a dominant wavelength of 558 nm. Upon oxidation the color changes to a light grey-green located near the illumination source. By replacing the electron-rich EDOT with a thiophene to form PBTh-PyrPyr-Ph 2 , the neutral polymer is a different color (lavender, l d = 475) that becomes baby blue upon oxidation. 4.8 Summary and Discussion The results presented herein show that increasing the acceptor content from pyridine to pyrido[3,4b ]pyrazine is a successful way to modulate LUMO levels to control both optical and electrochemical properties. In addition, in order to access these states electrochemically, it has been shown that proper choice of the electrolyte salt is imperative to adequately discern whether a true doping occurs or merely a redox-type process. To correctly discern this, simply performing voltammetry or conductance measurements are inadequate; rather spectroelectrochemistry is necessary to characterize the reduced state. Unfortunately, the vast majority of work in the field of low gap n-type dopable polymers only performs cyclic voltammetry and mistakenly assigns n-type doping to simple reduction processes. A summary of electrochemical and optical data is shown in Table 4-1. Poly( 1 ) is a bright red in its neutral form for all four electrolytes examined in these studies. Upon

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108 oxidation, the polymer films switch from red to a blue-purple color, and for all four electrolytes examined. Upon reduction, however, a color change is evident only when TBA + and TEA + are used as counter cations. The use of the alkaline cations, Na + and Li + , display no color changes upon application of reducing potentials. Based on color change Figure 4-25. Colorimetry of films of poly( 1 ), poly( 2 ), and poly( 9 ) on ITO-coated glass slides in 0.1 M tetran -butylammonium perchlorate/acetonitrile solution.

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109 only as an indicator of a doping process, the researcher would assign the electrochemical responses seen with the n -alkylammonium salts as n-type doping. Assigning n-type doping to the reduction behavior of poly( 1 ) mirrors the color changes results. For the alkaline cations, no electrochemical response is seen; therefore, doping must not be occurring. With TBA + and TEA + used as the electrolytes, a current response is seen with a discernable E 1/2 value, so n-type doping must be occuring. DPV results mirror the cyclic voltammetry results. Examination of the conductance measurements, further reinforce the assumption that a current response upon reduction is indicative for n-type doping. Conductance increases occur for the TBA + and TEA + electrolytes to within one order of magnitude for p-type doping conductances with TBA + . A small peak is seen for Na + and none for Li + . For TBA + , p-typed doping spectroelectrochemistry shows depletion of the p p * transition and formation of polaron and bipolaron charge carriers upon doping. When reducing potentials are applied, the p p * transition is bleached, and the formation of intermediate charge carriers occurs. By changing to the TEA + electrolyte, p-type doping behavior upon oxidation is seen, and when reducing potentials are applied, formation of both polaron and bipolaron charge carriers occurs. With Na + and Li + , poly( 1 ) can only be p-type doping as no charge carriers form upon complete reduction. For poly( 1 ), the simple assumption that CV is only needed to assign doping behavior works; however, by examining the CV, DPV, conductance, UV-Vis-NIR, and color switching behavoir of poly( 2 ), this assumption proves incorrect. Poly( 2 ) displays current responses upon reduction for both the CV and DPV experiments with all

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110 electrolytes except Li + . The mistake now would be to assume this is n-type doping without further experiments. Examination of the conductance experiments for poly( 2 ) show that two increases of conductivity occur for TBA + and TEA + , mirroring the CV and DPV results. Use of Na + as the electrolyte yields only one increase in conductance. Only a small peak is seen when Li + is used. Based on the CV, DPV, and conductance changes, most researchers would assign the electrochemical responses as n-type doping for TBA + , TEA + , and Na + . Color changes upon reduction for poly( 2 ) when TBA + is used as the counter ion are from a lime green neutral to a burgundy upon first reduction and a dark gray upon second reduction. When TEA + , Na + , and Li + are used as the electrolytes, the neutral lime green is converted to bright orange when reduction potentials are applied. The majority of researchers would assign this color change to a n-type doping process. However, examination of spectroelectrochemical results are imperative to correctly assign these processes to doping or simple redox behavior. Application of reduction potentials to poly( 2 ) with TBA + present leads to the formation of charge carriers. However, with TBA + , TEA + , and Na + , no charge carrier formation is evident. The color change occurs due to formation of a absorption band at 2.3 eV. Therefore, n-type doping only occurs for TBA + and not TBA + , TEA + , and Na + . To date relatively few studies of the reduced state of conjugated polymers have used spectroelectrochemistry as a means to assign reduction as n-type doping. 21 The polymers examined in these 13 reports use spectroelectrochemistry and show charge carrier formation upon reduction of the systems studied. Further work on the systems detailed in here is currently being undertaken. Polymerization of the thiophene-based D-A-D monomers using boron trifluoride-diethyl

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111 etherate as a means to lower the oxidation potential of the monomer and create less defect sights is underway. Further attempts to electropolymerize the TMS-substituted monomers in the presence of potassium fluoride or tetran -butylammonium fluoride to give better polymer film deposition on ITO is also under study. Spectroelectrochemistry of the reduced state in the presence of varying electrolytes with other donor-acceptors systems previously studied by our group are being undertaken. Examination of the reduced state in the mid and far IR to better understand n-type doping are being performed in collaboration with Prof. David Tanner’s group. Soluble polymers based on alkyl-substituted ProDOT’s are being prepared as copolymers with functionalized pyridines to modulate the electrochemical and optical properties of these systems. 21. (a) Ahonen, H. J.; Lukkari, J.; Kankare, J. Macromolecules 2000 , 33 , 6787-6793. (b) Aizawa, M.; Watanabe, S.; Shinohara, H.; Shirakawa, H. J. Chem. Soc., Chem. Commun. 1985 , 264-265. (c) Barbarella, G.; Favaretto, L.; Sotgiu, G.; Zambianchi, M.; Arbizzani, C.; Bongini, A.; Mastragostino, M. Chem. Mater. 1999 , 11 , 2533-2541. (d) Bongini, A.; Barbarella, G.; Favaretto, L.; Zambianchi, M.; Mastragostino, M.; Arbizzani, C.; Soav, F. Synth. Met. 1999 , 101 , 13-14. (e) Cravino, A.; Neugebauer, H.; Luzzati, S.; Catellani, M.; Sariciftci, N. S. J. Phys. Chem. B 2001 , 105 , 46-52. (f) Karikomi, M.; Kitamura, C.; Tanaka, S.; Yamashita, Y. J. Am. Chem. Soc. 1995 , 117 , 6791-6792. (g) Kitamura, C.; Tanaka, S.; Yamashita, Y. Chem. Mater. 1996 , 8 , 570-578. (h) Lee, B.-L.; Yamamoto, T. Macromolecules 1999 , 32 , 1375-1382. (i) Onoda, M.; Morita, S.; Iwasa, T.; Nakayama, H.; Yoshino, K. J. Phys. D: Appl. Phys 1991 , 24 , 1658-1664. (j) Onoda, M.; Morita, S.; Iwasa, T.; Nakayama, H.; Yoshino, K. Jpn. J. Appl. Phys. 1992 , 31 , 1107-1111. (k) Onoda, M.; Nakayama, H.; Morita, S.; Yoshino, K. J. Electrochem. Soc. 1994 , 141 , 338-341. (l) Schenk, R.; Gregorius, H.; M llen, K. Adv. Mater. 1991 , 3 , 492-493. (m) Yamamoto, T.; Sugiyama, K.; Kushida, T.; Inoue, T.; Kanbara, T. J. Am. Chem. Soc. 1996 , 118 , 39303937.

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112 Table 4-1. Summary of electrochemical results and color swatches for poly( 1 ) and poly( 2 ). Polymer (electrolyte) E 1/2 (ox) a E 1/2 (red) oxidized color neutral color reduced color p-doping/ n-doping 1 , TBAP +0.9 -1.8 Yes/Yes 1 , TEAP +1.0 -1.8 Yes/Yes 1 , NaP +0.9 Yes/Yes 1 , LiP +1.0 Yes/No 2 , TBAP -1.0, -1.7 Yes/No 2 , TEAP -1.0, -1.5 Yes/No 2 , NaP -1.1, -1.6 Yes/No 2 , LiP -, Yes/No a. Where values are not shown, E 1/2 values where not disecernable, but p-type doping occurs.

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113 APPENDIX A SELECTED NMR AND UV-VIS DATA Figure A-1. 1 H NMR spectrum of (2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)-trimethylstannane in CDCl 3 Figure A-2. 13 C NMR spectrum of (2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)-trimethylstannane in CDCl 3

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114 Figure A-3. 1 H NMR spectrum of trimethyl-(7-trimethylstannanyl-2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)-silane in CDCl 3 Figure A-4. 1 H NMR spectrum of trimethyl-(7-trimethylstannanyl-2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)-silane in CDCl 3

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115 Figure A-5. 13 C NMR spectrum of 2,3,4,5-tetrabromothiophene in CDCl 3

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116 Figure A-6. 1 H NMR spectrum of 3,4-dibromothiophene in CDCl 3 Figure A-7. 13 C NMR spectrum of 3,4-dibromothiophene in CDCl 3

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117 Figure A-8. 1 H NMR spectrum of 3,4-dimethoxythiophene in CDCl 3 Figure A-9. 13 C NMR spectrum of 3,4-dimethoxythiophene in CDCl 3

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118 Figure A-10. 1 H NMR spectrum of 3,3-dimethyl-3,4-dihydro-2 H -thieno[3,4b ][1,4]dioxepine in CDCl 3 Figure A-11. 13 C NMR spectrum of 3,3-dimethyl-3,4-dihydro-2 H -thieno[3,4b ][1,4]dioxepine in CDCl 3

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119 Figure A-12. 1 H NMR spectrum of 2,5-bis-trimethylsilanyl-thiophene in CDCl 3 Figure A-13. 13 C NMR spectrum of 2,5-bis-trimethylsilanyl-thiophene in CDCl 3

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120 Figure A-14. 1 H NMR spectrum of 2,3-diphenyl-pyrido[3,4b ]pyrazine in CDCl 3 Figure A-15. 13 C NMR spectrum of 2,3-diphenyl-pyrido[3,4b ]pyrazine in CDCl 3

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121 Figure A-16. 1 H NMR spectrum of 2,5-dibromopyridine-3,4-diamine in DMSOd 6 . Figure A-17. 13 C NMR spectrum of 2,5-dibromopyridine-3,4-diamine in DMSOd 6 .

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122 Figure A-18. 1 H NMR spectrum of 5,8-dibromo-2,3-diphenyl-pyrido[3,4b ]pyrazine in CDCl 3 Figure A-19. 13 C NMR spectrum of 5,8-dibromo-2,3-diphenyl-pyrido[3,4b ]pyrazine in CDCl 3

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123 Figure A-20. 1 H NMR spectrum of 3-amino-pyrazine-2-carboxylic acid methyl ester in CDCl 3

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124 Figure A-21. 13 C NMR spectrum of 3-amino-pyrazine-2-carboxylic acid methyl ester in CDCl 3 Figure A-22. 1 H NMR spectrum of 3-amino-6-bromo-pyrazine-2-carboxylic acid

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125 Figure A-23. 13 C NMR spectrum of 3-amino-6-bromo-pyrazine-2-carboxylic acid

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126 Figure A-24. 1 H NMR spectrum of 5-bromo-pyrazine-2-ylamine in CDCl 3 Figure A-25. 13 C NMR spectrum of 5-bromo-pyrazine-2-ylamine in CDCl 3

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127 Figure A-26. 1 H NMR spectrum of 3-chloropyrazine-1-oxide in CDCl 3 Figure A-27. 13 C NMR spectrum of 3-chloropyrazine-1-oxide in CDCl 3

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128 Figure A-28. 1 H NMR spectrum of 2,5-bis-(2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)pyridine in CDCl 3 Figure A-29. 13 C NMR spectrum of 2,5-bis-(2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)pyridine in CDCl 3

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129 Figure A-30. UV-Vis spectrum of 64 m M 2,5-bis-(2,3-dihydro-thieno[3,4b ][1,4]dioxin-5yl)-pyridine in methylene chloride

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130 Figure A-31. 1 H NMR spectrum of 5,8-bis-(2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)pyrido[3,4b ]pyrazine in CDCl 3

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131 Figure A-32. 1 H NMR spectrum of 5,8-bis(2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)2,3-diphenyl-pyrido[3,4b ]pyrazine in CDCl 3 Figure A-33. 13 C NMR spectrum 5,8-bis(2,3-dihydro-thieno[3,4b ][1,4]dioxin-5-yl)-2,3diphenyl-pyrido[3,4b ]pyrazine in CDCl 3

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132 Figure A-34. UV-Vis spectrum of 1.8 m M 5,8-bis(2,3-dihydro-thieno[3,4b ][1,4]dioxin-5yl)-2,3-diphenyl-pyrido[3,4b ]pyrazine in methylene chloride

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133 Figure A-35. 1 H NMR spectrum of 2,5-bis-(3,3-dimethyl-3,4-dihydro-2 H -thieno[3,4b ][1,4]dioxepin-6-yl)-pyridine in CDCl 3

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134 Figure A-36. 13 C NMR spectrum of 2,5-bis-(3,3-dimethyl-3,4-dihydro-2 H -thieno[3,4b ][1,4]dioxepin-6-yl)-pyridine in CDCl 3

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135 Figure A-37. UV-Vis spectrum of 2.8 m M 2,5-bis-(3,3-dimethyl-3,4-dihydro-2 H thieno[3,4b ][1,4]dioxepin-6-yl)-pyridine in methylene chloride

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136 Figure A-38. 1 H NMR spectrum of 5,8-bis-(3,3-dimethyl-3,4-dihydro-2 H -thieno[3,4b ][1,4]dioxepine-6-yl)-2,3-diphenyl-pyrido[3,4b ]pyrazine in CDCl 3 Figure A-39. 13 C NMR spectrum of 5,8-bis-(3,3-dimethyl-3,4-dihydro-2 H -thieno[3,4b ][1,4]dioxepine-6-yl)-2,3-diphenyl-pyrido[3,4b ]pyrazine in CDCl 3

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137 APPENDIX B CRYSTALLOGRAPHIC INFORMATION FOR MONOMERS Figure B-1. Crystal data and structure refinement for BEDOT-PyrPyr-Ph 2 . R 1 F 0 F c – () F 0 -------------------------------------= wR 2 wF 0 2 F c 2 – () 2 [] wF 0 2 () 2 [] ----------------------------------------12 w 1 s 2 F 0 2 () 0.0370 p () 2 0.31 p + + [] --------------------------------------------------------------------------------------= , =

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138 Empirical formula C 31 H 21 N 3 O 4 S 2 Formula weight 563.63 Temperature 173(2) K Wavelength 0.71073 Crystal system Orthorhombic Space group P2(1)2(1)2(1) Unit cell dimensions a = 6.9264(5) a = 90 b = 18.077(12) b = 90 c = 20.0393(13) g = 90 Volume 2509.1(3) 3 Z 4 Density (calculated) 1.492 Mg/m 3 Absorption coefficient 0.259 mm -1 F(000) 1168 Crystal size 0.15 x 0.15 x 0.08 mm 3 Theta range for data collection 1.52 to 25.00 Index ranges Reflections collected 13405 Independent reflections 4395 [R(int) = 0.0574] Completeness to theta = 27.49 100.0 % Absorption correction Integration Max. and min. transmission 0.9848 and 0.9594 Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 4395 / 0 / 361 Goodness-of-fit on F 2 1.135 Final R indices [I>2sigma(I)] R1 =0.0532 , wR2 = 0.1192 [3945] R indices (all data) R1 = 0.0620, wR2 = 0.1253 Absolute structure parameter -0.02(11) Largest diff. peak and hole 0.353 and -0.277 e. -3 S wF 0 2 F c 2 – () 2 () np – () ----------------------------------------12 p ma xF 0 2 0 , () 2 F c 2 + [] 3 -----------------------------------------------------= , = 8 – h 7 21 k 1 9 23 – l 18 , – ,

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139 Table B-1. Atomic coordinates (x 10 4 ) and equivalent isotropic displacement parameters ( 2 x 10 3 ) for BEDOT-PyrPyr-Ph 2 . U(eq) is defined as one third of the trace of the orthogonalized U ij tensor x y z U(eq) S1 9953(2) 938(1) 721(1) 34(1) S2 5585(2) 2298(1) 4102(1) 36(1) O1 7590(4) 1416(2) -982(1) 39(1) O2 5221(4) 1883(1) 128(1) 33(1) O3 1552(4) 2901(2) 2867(1) 33(1) O4 901(5) 3460(2) 4208(2) 49(1) N1 9388(5) 919(2) 2107(2) 28(1) N2 7700(5) 1359(2) 3301(2) 28(1) N3 4631(5) 2305(2) 2110(2) 40(1) C1 6015(6) 1935(2) -1055(2) 37(1) C2 4489(7) 1770(2) -542(2) 39(1) C3 9743(6) 983(2) -136(2) 35(1) C4 8146(6) 1322(2) -330(2) 28(1) C5 6951(6) 1553(2) 219(2) 29(1) C6 7755(5) 1407(2) 837(2) 27(1) C7 7008(6) 1614(2) 1490(2) 27(1) C8 5456(6) 2075(2) 1532(2) 27(1) C9 5335(5) 2079(2) 2708(2) 27(1) C10 4467(6) 2371(2) 3316(2) 29(1) C11 2793(6) 2772(2) 3382(2) 31(1) C12 2470(6) 3036(2) 4052(2) 33(1) C13 3837(7) 2827(2) 4475(2) 40(1) C14 -52(7) 3755(3) 3626(2) 50(1) C15 -279(6) 3169(3) 3123(2) 44(1) C16 6961(6) 1592(2) 2709(2) 26(1) C17 7821(6) 1368(2) 2103(2) 26(1)

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140 Table B-1. Continued x y z U(eq) C18 10110(6) 697(2) 2687(2) 27(1) C19 9235(6) 938(2) 3305(2) 28(1) C20 9970(6) 743(2) 3984(2) 29(1) C21 8665(6) 473(2) 4443(2) 32(1) C22 9290(7) 292(2) 5085(2) 36(1) C23 11181(7) 388(2) 5262(2) 37(1) C24 12478(7) 688(2) 4807(2) 37(1) C25 11879(6) 858(2) 4168(2) 33(1) C26 11806(6) 194(2) 2657(2) 29(1) C27 13229(6) 312(2) 2173(2) 36(1) C28 14820(7) -152(2) 2145(2) 41(1) C29 14992(7) -741(2) 2588(2) 45(1) C30 13561(7) -864(2) 3055(2) 41(1) C31 11990(7) -409(2) 3087(2) 35(1)

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141 Table B-2. Bond lengths [] for BEDOT-PyrPyr-Ph 2 . . Bond Bond Distance ( ) Bond Bond Distance ( ) S1-C3 1.727(4) C6-C7 1.454(5) S1-C6 1.757(4) C7-C8 1.363(5) S2-C13 1.714(4) C7-C17 1.424(5) S2-C10 1.761(4) C8-H8A 0.9500 O1-C4 1.372(5) C9-C16 1.430(5) O1-C1 1.446(5) C9-C10 1.457(5) O2-C5 1.351(5) C10-C11 1.374(5) O2-C2 1.450(5) C11-C12 1.441(5) O3-C11 1.363(5) C12-C13 1.327(6) O3-C15 1.451(5) C13-H13A 0.9500 O4-C12 1.366(5) C14-C15 1.471(6) O4-C14 1.443(5) C14-H14A 0.9900 N1-C18 1.326(5) C14-H14B 0.9900 N1-C17 1.355(5) C15-H15A 0.9900 N2-C19 1.307(5) C15-H15B 0.9900 N2-C16 1.360(5) C16-C17 1.410(5) N3-C9 1.356(5) C18-C19 1.447(5) N3-C8 1.357(5) C18-C26 1.447(5) C1-C2 1.504(6) C19-C20 1.494(5) C1-H1A 0.9900 C20-C21 1.379(6) C1-H1B 0.9900 C20-C25 1.388(6) C2-H2A 0.9900 C21-C22 1.396(5) C2-H2B 0.9900 C21-H21A 0.9500 C3-C4 1.323(6) C22-C23 1.368(6) C3-H3A 0.9500 C22-H22A 0.9500 C4-C5 1.438(5) C23-C24 1.391(6) C5-C6 1.385(5) C23-H23A 0.9500

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142 Table B-2. Continued Bond Bond Distance ( ) Bond Bond Distance ( ) C24-C25 C28-C29 1.390(6) C24-H24A C28-H28A 0.9500 C25-H25A C29-C30 1.382(7) C26-C31 C29-H29A 0.9500 C26-C27 C30-C31 1.365(6) C27-C28 C30-H30A 0.9500 C27-H27A C31-H31A 0.9500

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143 Table B-3. Bond angles[] for BEDOT-PyrPyr-Ph 2 . Atoms Bond Angle () Atoms Bond Angle () C3-S1-C6 92.09(19) O2-C5-C6 124.2(4) C13-S2-C10 92.20(19) O2-C5-C4 122.4(3) C4-O1-C1 112.9(3) C6-C5-C4 113.4(4) C5-O2-C2 111.9(3) C5-C6-C7 127.7(4) C11-O3-C15 110.0(3) C5-C6-S1 108.8(3) C12-O4-C14 112.7(3) C7-C6-S1 123.4(3) C18-N1-C17 119.2(3) C8-C7-C17 116.7(3) C19-N2-C16 119.4(3) C8-C7-C6 119.6(3) C9-N3-C8 120.7(3) C17-C7-C6 123.7(4) O1-C1-C2 109.4(3) N3-C8-C7 124.9(3) O1-C1-H1A 109.8 N3-C8-H8A 117.6 C2-C1-H1A 109.8 C7-C8-H8A 117.6 O1-C1-H1B 109.8 N3-C9-C16 118.0(3) C2-C1-H1B 109.8 N3-C9-C10 118.8(3) H1A-C1-H1B 108.2 C16-C9-C10 123.2(3) O2-C2-C1 111.1(4) C11-C10-C9 128.3(3) O2-C2-H2A 109.4 C11-C10-S2 108.9(3) C1-C2-H2A 109.4 C9-C10-S2 122.7(3) O2-C2-H2B 109.4 O3-C11-C10 123.3(3) C1-C2-H2B 109.4 O3-C11-C12 123.4(3) H2A-C2-H2B 108.0 C10-C11-C12 113.3(3) C4-C3-S1 112.6(3) C13-C12-O4 125.5(4) C4-C3-H3A 123.7 C13-C12-C11 113.0(4) S1-C3-H3A 123.7 O4-C12-C11 121.5(4) C3-C4-O1 124.8(4) C12-C13-S2 112.6(3) C3-C4-C5 113.0(3) C12-C13-H13A 123.7 O1-C4-C5 122.0(4) S2-C13-H13A 123.7

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144 Table B-3. Continued Atoms Bond Angle () Atoms Bond Angle () O4-C14-C15 109.7(4) C20-C21-C22 120.2 O4-C14-H14A 109.7 C20-C21-H21A 120.2 C15-C14-H14A 109.7 C22-C21-H21A 120.4(4) O4-C14-H14B 109.7 C23-C22-C21 119.8 C15-C14-H14B 109.7 C23-C22-H22A 119.8 H14A-C14-H14B 108.2 C21-C22-H22A 119.8(4) O3-C15-C14 112.9(4) C22-C23-C24 120.1 O3-C15-H15A 109.0 C22-C23-H23A 120.1 C14-C15-H15A 109.0 C24-C23-H23A 120.1(4) O3-C15-H15B 109.0 C25-C24-C23 120.0 C14-C15-H15B 109.0 C25-C24-H24A 120.0 H15A-C15-H15B 107.8 C23-C24-H24A 120.0(4) N2-C16-C17 120.2(3) C24-C25-C20 120.0 N2-C16-C9 119.2(3) C24-C25-H25A 120.0 C17-C16-C9 120.6(3) C20-C25-H25A 118.9(4) N1-C17-C16 120.3(3) C31-C26-C27 121.7(4) N1-C17-C7 120.6(3) C31-C26-C18 119.4(4) C16-C17-C7 119.1(3) C27-C26-C18 119.7(4) N1-C18-C19 120.1(3) C28-C27-C26 120.2 N1-C18-C26 116.6(3) C28-C27-H27A 120.2 C19-C18-C26 123.3(3) C26-C27-H27A 120.4(4) N2-C19-C18 120.7(3) C27-C28-C29 119.8 C31-C30-H30A 119.8 C30-C31-H31A 119.5 C29-C30-H30A 119.8 C26-C31-H31A 119.5

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145 Table B-4. Anisotropic displacement parameters ( 2 x 10 3 ) for BEDOT-PyrPyr-Ph 2 . The anisotropic displacement factor exponent takes the form: -2 p 2 [ h 2 a* 2 U 11 + ... + 2 h k a* b* U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 S1 31(1) 42(1) 28(1) -1(1) 4(1) 9(1) S2 34(1) 49(1) 24(1) -3(1) 0(1) 7(1) O1 50(2) 43(2) 24(2) 1(1) 3(1) 5(1) O2 39(2) 37(2) 23(1) -1(1) -2(1) 14(1) O3 30(2) 45(2) 25(1) -3(1) 1(1) 11(1) O4 45(2) 64(2) 37(2) -9(2) 7(2) 21(2) N1 31(2) 30(2) 23(2) -2(1) 1(1) 2(2) N2 33(2) 25(2) 26(2) 0(1) -1(1) 3(1) N3 47(2) 39(2) 33(2) 2(2) 2(2) 10(2) C1 46(3) 36(2) 28(2) 7(2) 1(2) 8(2) C2 45(3) 41(2) 30(2) 0(2) -6(2) 13(2) C3 38(2) 45(2) 23(2) -2(2) 10(2) -1(2) C4 40(2) 25(2) 20(2) 2(2) 0(2) -1(2) C5 37(2) 24(2) 27(2) 0(2) -3(2) 3(2) C6 28(2) 25(2) 28(2) -3(2) 4(2) 3(2) C7 32(2) 27(2) 23(2) 0(2) 2(2) 0(2) C8 35(2) 30(2) 15(2) 0(2) -3(2) 8(2) C9 30(2) 28(2) 23(2) 0(2) 2(2) 2(2) C10 35(2) 31(2) 20(2) 4(2) 3(2) 1(2) C11 32(2) 32(2) 27(2) 0(2) 2(2) -2(2) C12 32(2) 33(2) 34(2) -9(2) 8(2) 0(2) C13 47(3) 48(3) 25(2) -4(2) 9(2) 5(2) C14 39(3) 59(3) 53(3) -8(2) 3(2) 24(2) C15 29(2) 63(3) 39(2) 4(2) 1(2) 10(2) C16 31(2) 26(2) 22(2) -1(2) 1(2) 3(2) C17 27(2) 28(2) 24(2) -2(2) 2(2) 4(2)

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146 Table B-4. Continued U 11 U 22 U 33 U 23 U 13 U 12 C18 29(2) 26(2) 26(2) 1(2) -3(2) -3(2) C19 29(2) 24(2) 29(2) 0(2) 0(2) -2(2) C20 37(2) 24(2) 24(2) -4(1) -4(2) 3(2) C21 31(2 33(2) 31(2) -1(2) 2(2) 0(2) C22 50(3) 33(2) 24(2) 1(2) 2(2) -1(2) C23 48(3) 37(2) 26(2) -2(2) -9(2) 2(2) C24 38(3) 39(2) 34(2) -2(2) -12(2) 0(2) C25 40(2) 30(2 30(2) 3(2) 2(2) 0(2) C26 32(2) 28(2) 28(2) -7(2) -5(2) 5(2) C27 36(2) 40(2) 30(2) -1(2) -1(2) 1(2) C28 33(2) 56(3) 36(2) -8(2) 1(2) 6(2) C29 38(2) 51(3) 46(3) -17(2) -5(2) 18(2) C30 60(3) 32(2) 30(2) -7(2) -16(2) 20(2) C31 45(3) 33(2) 28(2) -2(2) -2(2) 4(2)

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147 APPENDIX C POLY(DIOXYTHIOPHENE) INTELLECTUAL PROPERTY Hole Transport Layers for LEDs Friend, R. H.; Burroughes, J. H.; Kimura, M.; Heeks, S. K. Electroluminescent Devices. US Patent 6,429,601, August 6, 2002. Friend, R. H.; Pichler, K.; Lacey, D. J. Electroluminescent Device. US Patent 6,384,528, May 7, 2002. Gill, R. E.; Liedenbaum, C. T. H. F.; Wuijts, M. C. Electroluminescent Display Screen for Displaying Fixed and Segmented Patterns, and Method of Manufacturing Such an Electroluminescent Display Screen. US Patent 6,280,909, August 28, 2001. Harrison, N.; Tessler, N.; May, P. Organic EL Devices and Operation Therof. US Patent 6,002,206, December 14, 1999. Heeks, S. K.; Carter, J. C. Sputter Deposition. US Patent 6,559,593, May 6, 2003. Heeks, S. K.; Wittmann, H. F. Electroluminescent Devices with Voltage Drive Scheme. US Patent 5,965,901, October 12, 1999. Hikmet, R. A. M.; Braun, D. B.; Staring, A. G. J.; Schoo, H. F. M.; Lub, J. Electroluminescent Device Having Electroluminescent Compound and Liquid Crystalline Compound. US Patent 5,748,271, May 5, 1998. Jonas, F.; Karbach, A.; Muys, B.; van Thillo, E.; Wehrmann, R.; Elschner, A.; Dujardin, R. Conductive Coatings. US Patent 5,766,515, June 16, 1998. Jonas, F.; Elschner, A.; Wehrmann, R.; Quintens, D. Electroluminescent Arrangements. US Patent 6,376,105, April 23, 2002. Jonas, F.; Karbach, A.; Muys, B.; van Thillo, E.; Wehrmann, R.; Elschner, A.; Dujardin, R. Conductive Coatings. US Patent 6,083,635, July 4, 2000. Krijn, M. P. C. M.; Dona, M. J. J.; Swinkels, J. M. M.; Vleggaar, J. J. M. Flexible Substrate. US Patent 6,281,525, August 28, 2001.

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193 BIOGRAPHICAL SKETCH Charles Joseph DuBois, Jr. was born in Orange, Texas, on November 25th, 1974. He grew up in Gonzales, Louisiana, a small town situated between Baton Rouge and New Orleans. After graduating high school, he attended Louisiana State University and obtained his B. S. in chemistry along with a minor in history there. During that time he worked for Professor Robin McCarley and studied the electrochemistry and MALDI-TOF-MS of conjugated polymers. Upon graduation, he moved to Gainesville, Florida, to begin his graduate research inthe group of Professor John Reynolds and married Sonya Ducote (his high school sweetheart). At the University of Florida, he examined reduction of donor-acceptor conjugated polymers. Upon graduation, he will begin work in Wilmington, Delaware, as an employee of the DuPont Chemical Company.