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Visible‐light copper photocatalysis has recently emerged as a viable technology for building sustainable synthetic processes. To broaden the applications of phosphine‐ligated copper(I) complexes, we describe herein an effective metal‐organic framework (MOF)‐supported copper(I) photocatalyst for multiple iminyl radical‐mediated reactions. Due to site isolation, the heterogenized copper photosensitizer has a significantly higher catalytic activity than its homogeneous counterpart. Using a hydroxamic acid linker to immobilize copper species on MOF supports affords the heterogeneous catalysts with high recyclability. The post‐synthetic modification sequence on MOF surfaces allows for the preparation of previously unavailable monomeric copper species. Our findings highlight the potential of using MOF‐based heterogeneous catalytic systems to address fundamental challenges in the development of synthetic methodologies and mechanistic investigations of transition‐metal photoredox catalysis. [ABSTRACT FROM AUTHOR]

Under visible-light irradiation, this heterogenized copper(I) complex promotes multiple iminyl radical-mediated reactions initiated by N-O bond cleavage, with significantly enhanced photocatalytic activity compared to its homogeneous counterparts. Copper Photosensitizers, Hydroxamic Acids, Metal-Organic Frameworks, Photoredox Catalysis, Post-Synthetic Modification Keywords: Copper Photosensitizers; Hydroxamic Acids; Metal-Organic Frameworks; Photoredox Catalysis; Post-Synthetic Modification EN Copper Photosensitizers Hydroxamic Acids Metal-Organic Frameworks Photoredox Catalysis Post-Synthetic Modification 1 1 1 05/09/23 20230515 NES 230515 B A binap-ligated copper iodide dimer b embedded on a metal--organic framework (MOF) was designed as an effective photoredox catalyst by Dan Li, Jian He, and co-workers in their Research Article (e202300233). [Extracted from the article]

Copper Photosensitizers, Hydroxamic Acids, Metal-Organic Frameworks, Photoredox Catalysis, Post-Synthetic Modification Back Cover: Metal-Organic Framework Supported Copper Photoredox Catalysts for Iminyl Radical-Mediated Reactions (Angew. Keywords: Copper Photosensitizers; Hydroxamic Acids; Metal-Organic Frameworks; Photoredox Catalysis; Post-Synthetic Modification EN Copper Photosensitizers Hydroxamic Acids Metal-Organic Frameworks Photoredox Catalysis Post-Synthetic Modification 1 1 1 05/09/23 20230515 NES 230515 B A binap-ligated copper iodide dimer b embedded on a metal-organic framework (MOF) was designed as an effective photoredox catalyst by Dan Li, Jian He, and co-workers in their Research Article (e202300233). [Extracted from the article]