Aligning Metal Coordination Sites in Metal-Organic Framework- Enabled Metallaphotoredox Catalysis

Construction of catalytic metal centers, the key modules in artificial photosynthetic systems, lies at the heart to explore unpaved reactivity patterns powered by light. Here, we disclose that the amino (-NH2) and carboxylic (-COO) functionalities, aligned in various visible-light-harvesting metal- organic frameworks (MOFs) (NH2-UiO-66, (NH2)2-UiO-67, and NH2-MIL-125), provide N/O-ligated Ni featuring different configurations and valence states. Of note, these Ni centers, in situ formed or preimplanted, demonstrated coordination units' spatial arrangement-dependent activity in cross-coupling of aryl halides and various nucleophiles. Our work provides a novel approach to construct and to regulate metal center(s) by MOFs' skeleton defined coordination environments, highlighting exclusive potential in exploring the reactivity pattern of the hosted metals.

Automated summary

In this study, it is discovered that the amino and carboxylic functionalities in visible-light-harvesting metal-organic frameworks can form nickel ions, which exhibit different activities in cross-coupling reactions of aryl halides and nucleophiles. This work provides a new approach to construct and regulate metal centers by manipulating the coordination environments of MOFs.