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California State University, Northridge The Synthesis and Electrochemical Characterization of Phosphole Containing Oligomers and Polymers A thesis submitted in partial fulfillment of the requirements For the degree of Master of Science in Chemistry By Robert Pankow May 2015 The thesis of Robert Pankow is approved: ____________________________________ ______________ Dr. Eric Kelson Date ____________________________________ ______________ Dr. Yann Schrodi Date ____________________________________ _______________ Dr. Katsu Ogawa, Chair Date California State University, Northridge ii Acknowledgments I would like to thank my mother, father, sister, Judith, and John for their love and support in all of my endeavors. To my lifelong friends Henry, Addison, and Ryan, thank you. I would like to thank Dr. Katsu Ogawa for allowing me to work in his lab and giving me the chance to learn and grow as a student of chemistry. You are an excellent mentor, and I will forever cherish you as a teacher. You have provided me with knowledge and insight to tackle problems, both professional and personal. Also, thank you Kenny Cooper, for joining me in the battle against low yields or no yields. Without your help, this thesis would not be as complete. I would like to thank Steven Ruark, who synthesized enough starting material to get me through a Masters program. I would like to thank Drs. Yann Schrodi and Eric Kelson for being members of my thesis committee and for being excellent instructors. It was in your classrooms I was able to expand my knowledge of chemistry and gain direction as to what interested me chemically. I would like to thank Drs. Thomas Minehan, Jeff Charonnat, and Simon Garrett for their excellent instruction and for further expanding my knowledge of chemistry. Despite the knowledge I have gained, I will forever remain a student only seeking to learn more. Finally, I would like to thank Michelle Chan, who provided love and support during difficult times, and Jhauvy, Alex, Kaveh, Capek,Yehan, Zach Perez, and Jaime for their friendship. iii Table of Contents Signature Page ii Acknowledgments iii List of Figures vi List of Tables x Abstract xii Chapter 1. Introduction 1 1.1 π-Conjugated Polymers and Oligomers for Organic Photovoltaics 1 1.2 Pt-containing Poly(aryleneethynylenes) 6 1.3 Phosphole Oligomers 11 Chapter 2. Synthesis of Phosphole Oligomers and Derivatives 23 2.1 Synthesis of Butadienes 23 2.2 Synthesis of Phospholes 29 2.3 Synthesis of Phosphole Derivatives 39 Chapter 3. Electrochemical Characterization of Phospholes 43 Chapter 4. Phosphole-Pt Containing Poly(aryleneethynylenes) 52 4.1 Synthesis of Phosphole-Pt Containing Poly(aryleneethynylenes) 52 4.2 Electrochemistry of Phosphole-Pt poly(aryleneethynylenes) 56 Chapter 5. Conclusion 64 Chapter 6. Experimental 66 iv References 75 Appendix A: NMR and cyclic-voltammetry data for select compounds 79 v List of Figures Figure 1-1 Common π-conjugated polymers 2 Figure 1-2 Electron transfer from the donor to acceptor material in a 3 solar cell Figure 1-3 Modifying the substituents of the polymer backbone 5 Figure 1-4 Hagihara coupling to prepare Pt-containing poly-arylenes 7 Figure 1-5 Pt containing poly(phenyleneethylene) 8 Figure 1-6 Variation of the aryl linker for conjugated organometallic 9 polymers Figure 1-7 Common Heteroacenes 11 Figure 1-8 Fused ring system phosphole oligomers 13 Figure 1-9 Synthetic methods for the preparation of phospholes 14 Figure 1-10 Fused bithiophene and naptholene [c]-fused phospholes 15 Figure 1-11 Diacenanaptho[1,2-b:1’2’-d]phospholes 17 Figure 1-12 2,5-bis(aryl)phospholes studied by Réau 18 Figure 1-13 Fused bi-aryl phospholes and derivatives 20 Figure 2-1 Synthesis of butadienes via silane-homocoupling 23 Figure 2-2 Synthesis of butadienes via Wittig olefination 23 Figure 2-3 Palladacycles potentially derived from 2-pyridylhalides and 26 2-thiazolehalides. Figure2-4 Copper mediated homocoupling of substituted 27 pyridyldimethyl(vinyl)silanes Figure 2-5 Dimerization of 2H-phospholes 29 Figure 2-6 Rearrangement of 1,2,5-triarylphoshpoles 33 vi Figure 2-7 31P NMR spectra showing rearranged phosphole byproducts 34 for entries 5 (top) and 3 (bottom) of Table 2-4 Figure 2-8 31P NMR spectra showing dimer by products for entries 1 36 (top) and 4 (bottom) of Table 2-4 Figure 2-9 31P NMR spectra for Pt complexes 61a and 61b 42 Figure 3-1 Cyclic-voltammograms of compounds 17b, 49b, and 60b. 44 Measured in MeCN using Pt disk working electrode, Bu4NPF6 as the supporting electrolyte, and ferrocene as an internal standard Figure 3-2 Cyclic-voltammograms of phospholes 49a-c. Measured in 46 MeCN using Pt disk working electrode, Bu4NPF6 as the supporting electrolyte, and ferrocene as an internal standard Figure 3-3 Cyclic-voltammograms of complexes 61a,b. Measured in 50 DCM using Pt disk working electrode, Bu4NPF6 as the supporting electrolyte, and ferrocene as an internal standard Figure 3-4 Oxidative electropolymerisation of phosphole oxide 60b 51 (middle) and Pt complex 61b (right). The left panel shows decomposition of phosphole 49b. Measured in DCM using Pt disk working electrode, Bu4NPF6 as the supporting electrolyte, and ferrocene as an internal standard Figure 4-1 1H NMR spectra for polymer 63b 54 Figure 4-2 31P NMR spectra for polymer 63b 54 Figure 4-3 1H NMR spectra for polymer 63a 55 Figure 4-4 31P NMR spectra for polymer 63a 55 Figure 4-5 From top to bottom, cyclic-voltammograms of phosphole 58 ligands 49a,b, Pt complexes 61a,b, and polymers 63a,b. Measured in DCM using Pt disk working electrode, Bu4NPF6 as the supporting electrolyte, and ferrocene as an internal standard Figure 4-6 Cyclic-voltammograms of polymers 63a,b. Measured in DCM 59 using Pt disk working electrode, Bu4NPF6 as the supporting electrolyte, and ferrocene as an internal standard vii Figure 4-7 Cyclic-voltammograms of polymers 63a,b were measured in 62 DCM using Pt disk working electrode, Bu4NPF6 as the supporting electrolyte, and ferrocene as an internal standard, and cyclic-voltammograms of polymer films prepared from 63a,b. aFilms were prepared by drop casting a solution of the polymer in CHCl3 onto ITO glass plates and measured in MeCN using Bu4NPF6 as the supporting electrolyte and ferrocene as an internal standard Figure A-1 1,2,5-triphenylphosphole 1H NMR Spectrum 79 Figure A-2 1,2,5-triphenylphosphole 13C NMR spectrum 80 Figure A-3 1,2,5-triphenylphosphole 31P NMR spectrum 81 Figure A-4 1,2,5-triphenylphosphole HSQC NMR spectrum 82 Figure A-5 2,5-bis(4-pyridyl)4-anisole phosphole 1H NMR spectrum 83 Figure A-6 2,5-bis(4-pyridyl)4-anisole phosphole 31P NMR spectrum 84 Figure A-7 2,5-bis(4-pyridyl)4-anisole phosphole COSY NMR Spectrum 85 Figure A-8 2,5-bis(4-pyridyl)4-anisole phosphole HMBC NMR 86 spectrum. Figure A-9 2,5-bis(4-pyridyl)4-anisole phosphole HMBC NMR 87 spectrum. Figure A-10 2,5-bis(4-pyridil)phenyl phosphole 1H NMR spectrum 88 Figure A-11 2,5-bis(4-pyridil)phenyl phosphole 13C NMR spectrum 89 Figure A-12 2,5-bis(4-pyridil)phenyl phosphole 31P NMR spectrum 90 Figure A-13 2,5-bis(4-pyridil)phenyl phosphole COSY NMR spectrum 91 Figure A-14 2,5-bis(4-pyridil)phenyl phosphole COSY NMR spectrum 92 Figure A-15 2,5-bis(2-thienyl)phenyl phosphole 1H NMR spectrum 93 Figure A-16 2,5-bis(2-thienyl)phenyl phosphole 13C NMR spectrum 94 Figure A-17 2,5-bis(2-thienyl)phenyl phosphole 31P NMR spectrum 95 viii Figure A-18 2,5-bis(2-thienyl)phenyl phosphole COSY NMR spectrum 96 Figure A-19 2,5-bis(2-thienyl)phenyl phosphole HSQC NMR spectrum 97 Figure A-20 1,2,5-tris(4-fluorophenyl)phosphole 1H NMR spectrum 98 Figure A-21 1,2,5-tris(4-fluorophenyl)phosphole 13C NMR spectrum 99 Figure A-22 1,2,5-tris(4-fluorophenyl)phosphole 31P NMR spectrum 100 Figure A-23 1,2,5-tris(4-fluorophenyl)phosphole 19F NMR spectrum 101 Figure A-24 1,2,5-tris(4-fluorophenyl)phosphole COSY NMR spectrum 102 Figure A-25 1,2,5-tris(4-fluorophenyl)phosphole HMBC NMR spectrum 103 Figure A-26 1,2,5-tris(4-fluorophenyl)phosphole HSQC NMR spectrum 104 Figure A-27 Figure A-27.Cyclic-voltammograms for compounds 17a,c- 105 60a,c ix List of Tables Table 1-1 Photophysical and Electrochemical data for [c]-fused phospholes 16 Table 1-2 Photophysical and Electrochemical data for Diacenanaptho[1,2- 17 b:1’2’-d]phospholes Table 1-3 Photophysical and electrochemical data for selected 2,5- 19 bis(aryl)phospholes Table 1-4 Photophysical and electrochemical data for compounds 32-37 21 Table 2-1 Synthesis of aryl substituted pyridyldimethyl(vinyl)silanes. 25 Table 2-2 Experimental data for the homocoupling of pyridyl(vinyl)silanes 27 Table 2-3 Dependence of phosphole yield and purity on the heat source 30 Table 2-4 Microwave assisted phosphole synthesis via McCormack reaction 31 Table 2-5 Phosphole 13C chemical shifts and coupling constants. 38 Table 2-6 Phosphole 1H chemical shifts and coupling constants. 38 Table 2-7 Experimental and NMR data for phosphole oxides. 40 Table 2-8 Synthesis of complexes 61a,b 41 Table 3-1 Electrochemical data for butadienes17a-c, phospholes 49a-c, and 45 phosphole oxides 60a-c. Measured in MeCN using Pt disk working electrode, Bu4NPF6 as the supporting electrolyte, and ferrocene as an internal standard Table 3-2 Electrochemical data for phospholes 49a-c and 27 and 28.
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  • Recent Progress Concerning the N-Arylation of Indoles

    Recent Progress Concerning the N-Arylation of Indoles

    molecules Review Review RecentRecent ProgressProgress Concerningconcerning the the NN-Arylation-Arylation of of Indoles Indoles Petr Oeser, Jakub Koudelka, Artem Petrenko and Tomáš Tobrman * Petr Oeser, Jakub Koudelka , Artem Petrenko and Tomáš Tobrman * Department of Organic Chemistry, University of Chemistry and Technology, 16628 Prague, Czech Republic; [email protected] of Organic (P.O.); Chemistry, [email protected] University of Chemistry (J.K.); [email protected] and Technology, 16628 (A.P.) Prague, Czech Republic; [email protected]* Correspondence: (P.O.); [email protected] [email protected] (J.K.); [email protected] (A.P.) * Correspondence: [email protected] Abstract: This review summarizes the current state-of-the-art procedures in terms of the prepara- Abstract:tion of N-arylindoles.This review summarizesAfter a short the intr currentoduction, state-of-the-art the transition-metal procedures-free in procedures terms of the available preparation for oftheN N-arylindoles.-arylation of After indoles a short are briefly introduction, discussed. the Th transition-metal-freeen, the nickel-catalyzed procedures and palladium-catalyzed available for the NN-arylation-arylation ofof indoles are brieflyboth discussed. discussed. In Then,the next the section, nickel-catalyzed copper-catalyzed and palladium-catalyzed procedures for the NN-arylation-arylation ofof indolesindoles areare bothdescribed. discussed. The final In the sectio nextn section,focuses copper-catalyzedon recent findings procedures in the field forof bio- the Nlogically-arylation active of indolesN-arylindoles. are described. The final section focuses on recent findings in the field of biologically active N-arylindoles. Keywords: N-arylation; indole; Buchwald–Hartwig amination; Ullmann condensation; Chan–Lam Keywords:coupling N-arylation; indole; Buchwald–Hartwig amination; Ullmann condensation; Chan– Lam coupling 1.