Construction of Heteroleptic Copper Complexes in Perylene Diimide-Based COFs for Heterogeneous Metallaphotoredox Catalysis

作者：Xia Wu, Jun Guo, Meng Sun, Tao Du, Debo Hao, Dongyi Liu, Deyang Wang, Songwei Wen, Jun Yin, Dan Li, Jian He · 发表于：Journal of the American Chemical Society · 年份：2026 · DOI：10.1021/jacs.5c17585 · 被引用次数：3 · 研究领域：Covalent Organic Framework Applications、CO2 Reduction Techniques and Catalysts、Metal-Organic Frameworks: Synthesis and Applications

Despite recent advances in developing diimine-containing copper photocatalysts for organic synthesis, further exploration of heteroleptic phenanthroline-ligated copper complexes remains challenging due to rapid ligand exchange in homogeneous solutions. Herein, we employ a framework-based heterogenization strategy to successfully synthesize such previously inaccessible copper complexes through postsynthetic modification. By integrating photoactive perylene diimide units into a one-dimensional covalent organic framework, the visible-light-driven oxo-azidation of styrenes can be accomplished with substantially reduced copper loadings in metallaphotoredox catalysis. Notably, our newly developed heterogeneous photocatalytic platform demonstrates that the reactive copper species facilitates the ketone formation step in the oxo-azidation without dissociation of one of the phenanthroline ligands. These findings highlight the potential of well-defined framework materials to address fundamental challenges in the synthesis of transition-metal complexes and enable detailed mechanistic studies that complement traditional homogeneous catalysis.