Visible light-driven superoxide generation by conjugated polymers for organic synthesis

Benefiting from their unique delocalized electronic structure, conjugated polymer-based semiconductors are widely applied in the fields of organic electronics, sensors, and biomedical applications. However, the photocatalytic properties of conjugated polymers have been seldom studied because of their unsuitable band structures. Herein, we creatively demonstrate that the band structures of conjugated polymers are strongly related to their degree of polymerization (DP), offering an effective strategy for the design of metal-free photocatalysts with tunable light absorption properties. Taking poly(3-hexylthiophene) (PHT) as an example, we show that PHT nanofibers with a suitable DP are a novel visible light-driven photocatalyst, which can readily convert molecular oxygen into superoxide ions. Benefiting from the high selectivity of the generated superoxides, the PHT nanofibers display outstanding activity for the aerobic oxidation of amines into imines with nearly 100% conversion and selectivity. This study offers a new strategy for the design of advanced conjugated polymer-based photocatalysts.