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Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
Aligning Metal Coordination Sites in Metal-Organic Framework-Enabled Metallaphotoredox Catalysis
Tianjiao Liu1,2, Chaoyuan Deng1,2, Di Meng1,2
1Key Laboratory of Photochemistry, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China.
Abstract:
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.
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