Metallaphotocatalytic Platforms Based on Covalent Organic Frameworks for Cross-Coupling Reactions

Cooperation of transition metal catalysis with photocatalysis is an emerging powerful approach to achieve coupling reactions for the synthesis of important chemicals. Owing to their facilely modulated structures and properties via reticular chemistry, photoactive covalent organic frameworks (COFs) arise quickly in building metallaphotocatalytic platforms targeting more efficient and sustainable protocol. In this Minireview, we summarize the recent advances in COFs-based (integrated) platforms to forge carbon-carbon/heteroatom (C, B, N, O, P, and S, etc.) bonds via a variety of cross-coupling reactions driven by light, with focuses on the engineering of COFs' backbone, as well as the organization mode of COFs and metal site promoted catalytic performance. We also highlight the essential role of the underlying electron/energy processes in metallated COFs platforms (M@COFs). Aiming to guide catalysts' design to achieve more efficient performance or currently challenging transformations, we give our perspectives in this under-developed yet promising field. Metallaphotocatalytic platforms based on covalent organic frameworks (COFs) have shown great promise in catalyzing cross-coupling reactions. The facilely modulated opt-electronic properties via reticular chemistry, and manageable COF-metal organization, open up new avenues to promote electron transfer (ET) or energy transfer (EnT) that drives the cooperative transition metal catalytic cycle, affording valuable coupling products at enhanced energy/atomic efficiency.image