Photocatalytic Phenylmethylamine Coupling Reaction of Organic–Inorganic Composites Based on Benzothiophene Polymers and TiO2

Benzothiophene polymers, as a class of novel organic semiconductor materials, exhibit significant potential in the field of photocatalysis due to their broad light-responsive range and tunable energy level structures. In this study, a benzothiophene-based polymer organic semiconductor (denoted as P42) was integrated with titanium dioxide (TiO2) via a simple sol–gel method, yielding an organic–inorganic hybrid material. This composite facilitates the modulation of energy level potentials and promotes the effective separation of photogenerated charges, thereby demonstrating remarkable synergistic catalytic performance in the photocatalytic oxidative coupling of benzylamines. By optimizing the ratio of organic to inorganic components and various photocatalytic reaction conditions, the hybrid material 1.7%P42-TiO2, containing 1.7 wt% of the dithiophene polymer without any metal cocatalysts, exhibited outstanding performance under an air atmosphere and visible light irradiation after 12 h. It achieved a yield of over 88.7% and a selectivity exceeding 89.8% in the synthesis of N-benzoylaniline, significantly surpassing the performance of pure TiO2 (52.9% yield, 54.9% selectivity) and P42 (54.4% yield, 54.9% selectivity). Structural and photophysical characterizations, including UV–Vis DRS, XRD, SEM, TEM, and EPR, reveal that the enhanced photocatalytic activity originates from broad visible-light absorption, improved charge separation, and well-matched energy levels. Mechanistic investigations suggest a synergistic pathway involving photoinduced hole oxidation and radical-mediated coupling. This work provides valuable insights and a reference for the solar-driven photocatalytic synthesis of nitrogen-containing platform molecules under mild conditions.