Universal Suzuki−Miyaura Catalyst-Transfer Polymerization for Precision Synthesis of Various Donor−Acceptor Conjugated (Co)polymers
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Living catalyst-transfer polymerization has revolutionized the field of polymer synthesis, but the polymer scope is rather narrow. Herein we report a universal Suzuki−Miyaura catalyst-transfer polymerization (SCTP) that covers a wide range of monomers from donor (D) to acceptor (A) (hetero)arenes, such as 3,4-propylenedioxythiophene, benzotriazole, quinoxaline, and 2,3-diphenylquinoxaline, by using rationally designed boronate monomers and commercially available Buchwald Pd G3 precatalysts. As a result, D/A polymers were prepared with controlled molecular weight and narrow dispersity in excellent yield. In addition, the use of RuPhos−Pd led to unprecedented controlled D−A statistical copolymerization, thereby modulating the HOMO energy level and band gap energy of the resulting copolymers. Furthermore, to demonstrate the living character of SCTP, various combinations of D−A and A−A block copolymers were successfully prepared by both sequential addition and simple one-shot methods.