Abstract

Directed synthesis of high-efficiency visible photoinduced Baeyer-Villiger oxidation catalysts is of primary significance. Here, the isopolymolybdate anion [β-Mo8O26]4- is for the first time encapsulated with the photosensitive metalloligand [Ru(bpy)2(H2dcbpy)]2+ (bpy = 2,2'-bipyridine; H2dcbpy = 2,2'-bipyridine-5,5'-dicarboxylic acid) to synthesize polyoxometalate@metal-organic frameworks, {(CdDMF)2[Ru(bpy)2(dcbpy)]3([β-Mo8O26])}·5DMF (Ru-Mo8). The composite photocatalyst Ru-Mo8 not only has a light absorption of 700 nm but also shortens the photogenerated electron transfer distances and accelerates charge and proton transfer. Ru-Mo8 can perform the Baeyer-Villiger oxidation with high selectivity and up to 96.7% yield under visible light (λ > 400 nm) irradiation. The turnover number and turnover frequency of the reaction were computed to be 967 and 548 h-1, respectively, and the apparent quantum yield was 6.84% by 425 nm. Simultaneously, the radical mechanism of Baeyer-Villiger oxidation of Ru-Mo8 in the O2/benzaldehyde system under visible light (λ > 400 nm) irradiation was proposed.

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