Although living catalyst-transfer polymerization has revolutionized the field of conjugated polymer synthesis, the polymer scope is rather narrow with a given catalyst system. Herein we report a highly efficient Suzuki−Miyaura catalyst-transfer polymerization (SCTP) using Buchwald Pd G3 precatalysts that covers a wide range of monomers from electron-rich (donor, D) to electron-deficient (acceptor, A) (hetero)arenes. Initially, we optimized boronates to modulate the reactivity and stability of the monomers. As a result, poly(3,4-propylenedioxythiophene), polybenzotriazole, polyquinoxaline, and poly(2,3-diphenylquinoxaline) were prepared with controlled molecular weight and narrow dispersity (&lt; 1.29) in excellent yield (&gt;85%). In addition, the use of RuPhos−Pd having excellent catalyst-transfer ability led to unprecedented controlled D−A statistical copolymerization, thereby modulating the HOMO energy level and band gap energy of the resulting copolymers. Moreover, the living nature of SCTP allowed to prepare various D−A and A−A block copolymers by the sequential addition method. Furthermore, simple but powerful one-shot D−A block copolymerization was achieved by maximizing the rate difference between the donor and acceptor monomers.

Controlled synthesis of strong donor/acceptor-based conjugated polymers and their (co)polymers via universal Suzuki−Miyaura catalyst-transfer polymerization

Fall 2022 abstracts, posters, and presentations will launch in mid-September.

ACS Fall 2022

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.