Metal-Organic Framework Supported Copper Photoredox Catalysts for Iminyl Radical-Mediated Reactions

Angew Chem Int Ed Engl. 2023 May 15;62(21):e202300233. doi: 10.1002/anie.202300233. Epub 2023 Mar 27.

Abstract

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.

Keywords: Copper Photosensitizers; Hydroxamic Acids; Metal-Organic Frameworks; Photoredox Catalysis; Post-Synthetic Modification.