Thiophene-Sulfone-Based D-A Conjugated Porous Polymers: Acceptor Regulation for Efficient Blue Light-Driven Selective Aerobic Oxidation of Sulfides and Amines.

Donor-acceptor (D-A)-type conjugated porous polymers (CPPs) have emerged as highly competitive photocatalysts for aerobic oxidation reactions. Herein, we rationally design and synthesize a series of D-A structured photocatalysts by employing dibenzothiophene-S, S-dioxide (BTDO) as the acceptor unit, and 4,8-bis(thiophen-2-yl) benzo [1,2-b:4,5-b'] dithiophene (DBD) and pyrene (Py) as the donor units. The effects of acceptor content on the optoelectronic and photocatalytic properties are systematically investigated. With the gradual increase in BTDO proportion and the decrease in pyrene content, the photocatalysts exhibit gradually narrowed band gaps, significantly promoted charge separation efficiency, and broadened visible light absorption range. Among the five as-prepared photocatalysts, DBD-T displays superior catalytic performance toward blue light-driven aerobic oxidation. Under mild conditions, benzyl sulfide and benzyl amine are selectively converted into benzyl sulfoxide and benzyl imine with a high conversion efficiency up to 96%. Moreover, DBD-T shows good universality toward a wide range of substrates, together with excellent recyclability and long-term stability. This work demonstrates that enhancing the electron-withdrawing capability of the acceptor unit represents a feasible and effective strategy to boost the photocatalytic performance of D-A-type conjugated polymers.