ABSTRACT The development of multifunctionally heterogeneous catalysts, simultaneously bearing photosensitizer and nonnoble metal catalyst in close spatial proximity, represents a promising solution for promoting metallaphotoredox‐mediated catalysis, albeit it remains challenging. Herein, a single‐site Ni‐functionalized photosensitive covalent organic framework (COF), TTA‐BPyDA(Ni)‐COF, has been constructed by implementing a postsynthetic metallization strategy in a triazine‐based COF scaffold. The precise integration of photosensitizer and Ni‐catalytic active centers within TTA‐BPyDA(Ni)‐COF not only dramatically improves the metallaphotocatalytic (MPC) performance in C─S/C─N cross‐coupling reaction between diverse thiols/amines and aryl iodides with electron‐rich/neutral/deficient groups but also confers TTA‐BPyDA(Ni)‐COF with outstanding recyclability and durability compared with its homogeneous counterpart. Importantly, the MPC C─S/C─N reaction mechanisms have been well established by comprehensive experimental and theoretical simulations. This work offers valuable insights for developing single‐site nonnoble metal‐functionalized COF catalytic platforms that integrate photoredox centers with catalytic transition‐metal cores.
Xiong et al. (Sat,) studied this question.