Acetylene/Vinylene‐Bridged π‐Conjugated Covalent Triazine Polymers for Photocatalytic Aerobic Oxidation Reactions under Visible Light Irradiation

Solar‐driven photocatalytic chemical transformation provides a sustainable strategy to produce valuable feedstock, but designing photocatalysts with high efficiency remains challenging. Herein, two acetylene‐ or vinylene‐bridged π‐conjugated covalent triazine polymers, A‐CTP‐DPA and V‐CTP‐DPE, were successfully fabricated toward metal‐free photocatalytic oxidation under visible light irradiation. Compared to the one without acetylene or vinylene bridge, both resulting polymers exhibited superior activity in photocatalytic selective oxidation of sulfides and oxidative coupling of amines; in particular, A‐CTP‐DPA delivered an optimal photocatalytic performance. The superior activity was attributed to the broadened spectral response range, effective separation, rapid transportation of photogenerated charge carriers, and abundant active sites for photogenerated electrons due to the existence of the acetylene bridge in the framework. This work highlights the potential of acetylene and vinylene bridges in tuning catalytic efficiency of organic semiconductors, providing a guideline for the design of efficient photocatalysts. Building bridges: Acetylene or vinylene‐bridged π‐conjugated covalent triazine polymers, A‐CTP‐DPA and V‐CTP‐DPE, are fabricated toward metal‐free photocatalytic oxidation under visible light irradiation. Impressively, compared to the one without acetylene or vinylene bridge, A‐CTP‐DPA and V‐CTP‐DPE exhibit superior activity in photocatalytic selective oxidation of sulfides and oxidative coupling of amines.