Synthesis of Comb-Shaped Polyvinylthiophenes with Anionic Polymerization of 5-Vinyl-2,2’-bithiophene (VBT) and Suzuki-Miyaura Cross-Coupling Reaction of Poly(VBT): Control of Intermolecular Interactions of Adjacent Side Chains

ABSTRACT Soluble comb-shaped polyvinylthiophenes with well-controlled and defined multifunctional side chains were synthesized for the first time. Poly(5-vinyl-2,2’-bithiophene) (PVBT) as a main chain was obtained successfully by a thoughtfully designed anionic polymerization of 5-vinyl-2,2’-bithiophene. Bromination and Suzuki-Miyaura cross-coupling of PVBT gave the desired multifunctional side chains in almost quantitative yield. The obtained polymers could be quickly and easily purified by reprecipitation. The insertion of a repelling unit in the side chain prevented strong π-π interactions between adjacent side chains and dramatically improved the solubility of the comb-shaped polyvinylthiophenes. The optical properties of these polymers were strongly influenced by the intermolecular interactions of adjacent side chains. These comb-shaped polyvinylthiophenes possessed good solubility in common organic solvents, adjustable optical (or electrical) properties, and the ability to form high-quality thin films.