Visible-Light-Induced Phenoxyl Radical-based Metal-Organic Framework for Selective Photooxidation of Sulfides

Phenoxyl radicals originating from phenols through oxidation or photoinduction are relatively stable and exhibit mild oxidative activity, which endows them with the potential for photocatalysis. Herein, a stable and recyclable metal-organic framework Zr-MOF-OH constructed of a binaphthol derivative ligand has been synthesized and functions as an efficient heterogeneous photocatalyst. Zr-MOF-OH shows fairly good catalytic activity and substrate compatibility toward the selective oxidation of sulfides to sulfoxides under visible light irradiation. Such irradiation of Zr-MOF-OH converts the phenolic hydroxyl groups of the binaphthol derivative ligand to phenoxyl radicals through excited state intramolecular proton transfer, and the excited state photocatalyst triggers the single-electron oxidation of the sulfide. No reactive oxygen species are produced in the photocatalytic process, and triplet O₂ directly participates in the reaction, endowing Zr-MOF-OH with wide substrate compatibility and high selectivity, which also proposes a promising pathway for the direct activation of substrates via phenoxyl radicals.