A porphyrin‐based porous organic polymer containing flexible chains for efficient heterogeneous photocatalysis

Porphyrin‐based porous organic polymers (Por‐POPs) are attracting increasing attention because of their potential in visible light photocatalysis. The distinctive attributes of Por‐POPs have been elucidated by investigating their response to specific reactions, such as the aerobic oxidation of sulfides. However, most researchers choose porphyrin molecules with relatively short peripheral substituent chains and strong stiffness to construct porphyrin‐based materials, especially Por‐POPS. Herein, we designed and prepared a flexible POP material H 2 Pp‐TAPM by incorporating extra π‐conjugated rigid units TAPM into a relatively flexible porphyrin monomer H 2 Pp through imine linkages. The POP synthesized in this study has demonstrated the ability to facilitate the transfer and dissociation of photogenerated electron–hole pairs, leading to the production of singlet oxygen 1 O 2 and superoxide radical anions O 2 ˙ − . These anions act as effective mediators for the selective aerobic oxidation of sulfides, resulting in the conversion of 99% and the selectivity more than 99%. Furthermore, the H 2 Pp‐TAPM has excellent stability and recyclability, indicating its attractiveness as heterogeneous photocatalyst for the transformation of organic compounds. This makes it a promising candidate for visible‐light‐driven reactions.