Vinylene-linked fully conjugated porous organic polymers based on difluoroboron β-diketonate complexes for green and efficient photocatalysis

Abstract

Nowadays, organic boron-containing dyes have garnered considerable interest as efficient photocatalysts owing to their advantages including large molar absorption coefficients, minimal bandgaps, and easy excitation. Incorporating various boron-containing dyes into porous organic polymers effectively addresses the issue of small boron-containing molecules, which are difficult to separate and prone to photobleaching. Nevertheless, the integration of boron-containing dyes into vinylene-linked conjugated porous organic polymers (POPs) remains unexplored. This study reports the synthesis of two distinct vinylene-linked fully conjugated POPs by reacting difluoroboron β-diketonate complexes with reactive methyl groups and a carbazole-bearing aldehyde. The formation of effective D–A interaction between the difluoroboron complexes and the carbazole subunit enhances charge transport and separation, thereby improving photocatalytic efficiency. CTBA-B2, with a higher content of the difluoroboron complex, exhibits superior catalytic activity in both oxidation and reduction reactions, and is capable of efficiently catalyzing sulfide oxidations as well as dehalogenation reactions in green ethanol solvents.