Xantphos–Cu‐Decorated Covalent Organic Frameworks for C─H Arylation through Sensitized Electron Transfer

The isoindolinone scaffold is an important structural motif found in a wide range of naturally occurring and synthetic biologically active compounds. However, the synthesis of isoindolinone derivatives typically requires multi‐step procedures or the use of palladium‐based catalysts, which are often hampered by low reaction yields and high costs. Recently, covalent organic frameworks (COFs)—emerging crystalline and porous materials—have gained considerable attention for their applications in various organic transformations, particularly in C─H functionalization, cross‐coupling and redox reactions. Although COFs have been extensively studied for photocatalysis, the development of sustainable heterogeneous catalysts using low‐cost transition metal‐based photosensitizers is still in its early stages. Herein, a strategy is presented to incorporate a copper‐Xantphos complex with a tetrahedral Cu(I) geometry into a crystalline and porous COF matrix. This modification enables unprecedented simultaneous electron and energy transfer efficiency during photocatalysis. The Cu–Xantphos coordinated COF exhibits potent photocatalytic activity for the synthesis of isoindolinone derivatives via C─Br and C─H bond cleavage followed by C─C bond formation. In addition, the catalyst shows excellent recyclability as it can be rejuvenated by reintroducing the Cu–Xantphos complex after multiple photocatalytic cycles—highlighting its potential as a sustainable and cost‐effective solution for valuable organic transformations.