Rational design of bimetallic sites in covalent organic frameworks for efficient photocatalytic oxidative coupling of amines

The conversion of organic compounds by photocatalysis under mild conditions is an environment-friendly alternative for organic transformations. In this work, the bimetallic covalent organic framework coordinated by Sr2+ and Fe2+ in the porphyrin centers with molar ratio of 2:1 (COF-Sr2Fe1) was synthesized through a two-step reaction. Under the synergistic regulation of Sr2+ and Fe2+, the separation of photogenerated charges and visible light absorption for COF-Sr2Fe1 were significantly promoted, and thus COF-Sr2Fe1 exhibited efficient photocatalytic performance towards benzylamine oxidative coupling reaction with a yield of 97 %, much higher than that of the nonmetallic covalent organic framework COF-366. Moreover, it was found that the Fe site displayed higher dehydrogenation ability and the Sr site displayed higher C-N coupling ability through the density functional theory (DFT) calculations, thereby making the dehydrogenation and C-N coupling steps more controllable for benzylamine oxidative coupling reaction by COF-Sr2Fe1. This work provides a strategy for designing efficient covalent organic frameworks photocatalysts, and helps to understand the oxidative coupling of amines more deeply.