Lewis Acid Regulation Strategy for Constructing D‐A‐A Covalent Organic Frameworks with Enhanced Photocatalytic Organic Conversion

Owing to their excellent photoelectric properties, donor‐acceptor (D−A) type photocatalytic covalent organic frameworks (COFs) have attracted significant research interest in recent years. However, the limited D−A structural units of existing COFs restrict the development of novel and efficient photocatalytic COF materials. To solve this problem, we developed a series of D−A‐A‐type COFs utilizing a Lewis acid regulation strategy, in which Lewis acids act as the coordination centers, and pyridine and cyano groups act as ligands. Lewis acid sites in COFs serve as electron acceptors, facilitating the separation and transfer of photogenerated electron‐hole pairs. This process is crucial for photocatalysis because it significantly increases the efficiency of the catalytic reaction by reducing the recombination rate of charge carriers. The developed Lewis acid‐activated D−A‐A COFs efficiently catalyzed the hydroxylation of various phenylboronic acid compounds under visible light. The developed catalysts are expected to contribute to increasing the fabrication efficiency of industrially important organic materials. A series of D−A‐A COFs are constructed by a novel Lewis acid regulatory strategy. In here, Lewis acid sites can be used as electron acceptors to facilitate the separation and transfer of h+−e− pairs and further increase optoelectronic properties. Among them, PYBP‐MgCl2‐COF exhibited the best activity for the visible light‐induced aerobic hydroxylation conversion of arylboronic acids with excellent yield and substrates compatibility.