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.

中文翻译：

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Ru 金属配体参与构建POM@MOF以增强可见光诱导 Baeyer-Villiger 氧化反应


高效可见光诱导 Baeyer-Villiger 氧化催化剂的定向合成具有重要意义。在这里，异多钼酸酯阴离子 [β-Mo₈O₂₆]^4– 首次被光敏金属配体 [Ru（bpy）₂（H₂dcbpy）]²⁺ （bpy = 2,2′-联吡啶;H₂dcbpy = 2,2′-联吡啶-5,5′-二羧酸）合成polyoxometalate@metal-有机框架，{（CdDMF）₂[Ru（bpy）₂（dcbpy）]₃（[β-Mo₈O₂₆]）}·5DMF （Ru-Mo₈）。复合光催化剂 Ru-Mo₈ 不仅具有 700 nm 的光吸收，而且缩短了光生电子转移距离并加速了电荷和质子转移。Ru-Mo₈ 可以在可见光 （λ > 400 nm） 照射下以高选择性和高达 96.7% 的产率进行 Baeyer-Villiger 氧化。计算出反应的转换数和转换频率分别为 967 和 548 ^h-1，表观量子产率为 6.84% x 425 nm。同时，提出了在可见光 （λ > 400 nm） 照射下 O₂/苯甲醛体系中 Ru-Mo₈ 的 Baeyer-Villiger 氧化的自由基机制。