Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R. China.
State Key Laboratory of Synthetic Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R. China.
Angew Chem Int Ed Engl. 2023 May 15;62(21):e202300233. doi: 10.1002/anie.202300233. Epub 2023 Mar 27.
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.
可见光铜光催化最近已成为构建可持续合成工艺的可行技术。为了拓宽膦配体铜（I）配合物的应用，我们在此描述了一种有效的金属有机骨架（MOF）负载铜（I）光催化剂，用于多种亚胺基自由基介导的反应。由于位阻隔离，异相铜敏化剂的催化活性明显高于其均相对应物。使用羟肟酸配体将铜物种固定在 MOF 载体上，得到具有高可回收性的非均相催化剂。在 MOF 表面进行的后合成修饰序列允许制备以前无法获得的单核铜物种。我们的发现强调了使用基于 MOF 的多相催化体系来解决合成方法学发展中的基本挑战以及过渡金属光还原催化的机理研究的潜力。
