A Carbazolyl Porphyrin‐Based Conjugated Microporous Polymer for Metal‐Free Photocatalytic Aerobic Oxidation Reactions

Abstract Herein, a carbazolyl porphyrin‐based π‐conjugated microporous polymer was prepared via simple FeCl 3 ‐catalyzed oxidative polymerization. The resulting polymer (TCPP‐CMP) exhibits high surface area, permanent pores, good stability, broad light absorption range and suitable redox potentials. As expected, TCPP‐CMP is a highly effective metal‐free and heterogeneous photocatalyst for a variety of aerobic oxidation reactions, including oxidative coupling of primary amines, oxidative dehydrogenation of secondary amines, and oxidation of sulfides into sulfoxides using molecular oxygen under visible light irradiation. Importantly, natural sunlight is able to promote the aerobic oxidation of benzylamine and thioanisole via TCPP‐CMP photocatalyst with high conversion and selectivity, which are comparable with reactions conducted under artificial light. In addition, heterogeneous TCPP‐CMP has good recyclability, which retained its activity even after four cycles. The current work lays the foundation for future applications of TCPP‐CMP as metal‐free heterogeneous photocatalyst for aerobic oxidation reactions.