Synthesis and Characterizations of Polythiophene Networks with Nonplanar BN Lewis Pair Building Blocks

Doping the boron (B) element endowed organic π-conjugated polymers (OCPs) with intriguing optoelectronic properties. Herein, we introduce a new series of thienylborane-pyridine (BN) Lewis pairs via the facile reactions between thienylborane and various pyridine derivatives. Particularly, we developed a "one-pot" synthetic protocol to access BN2 with an unstable 4-bromopyridine moiety. Polycondensations between the BN Lewis pairs and distannylated thiophene afforded a new series of BN-cross-linked polythiophenes (BN-PTs). Experiments revealed that BN-PTs exhibited highly uniform chemical structures, particularly the uniform chemical environment of B-centers. BN-PTs showed good stability in the solid state. PBN2 even maintained the uniform B-center under high temperature or moisture conditions. The studies further suggested that the presence of topological BN structures endowed the polymers with strong intramolecular charge separation character. As a proof of concept, a representative BN-PT was tested as the catalyst for photocatalytic hydrogen evolution.