Synthesis and characterization of novel regioregular polythiophenes, random copolymers of thiophene and studies of the GRIM polymerization method for the synthesis of polythiophenes

Presented here are studies of polythiophene homopolymers, random copolymers, and alternating copolymers. These polymers were synthesized by both a modified McCullough method and the GRIM method of polymerization. Additionally, reactivity studies of the GRIM polymerization of random copolymers are presented.; The work is presented in four experimental chapters. Chapter two details investigations of random copolymers synthesized by the GRIM method that include varying percentages of m-linked thiophene monomers for control of conjugation length and optical and electronic properties. Chapter three presents synthesis and characterization of novel homo- and alternating copolymers of thiophene substituted with short polysiloxanes. Chapter four includes reactivity studies of the GRIM polymerization method for copolymerizations of thiophenes. Finally, chapter five details two studies of polythiophenes, the first relating to perfluoroalkyl-substituted polythiophenes, and the second involving the post-polymerization functionalization of poly[3-(ω-bromohexyl)]thiophene.