Ru Metalloligands Participate in the Construction of POM@MOF for Enhancing the Visible Photoinduced Baeyer–Villiger Oxidation Reaction

IF 4.3 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Inorganic Chemistry Pub Date : 2024-12-17 DOI:10.1021/acs.inorgchem.4c03064

Luoning Li, Yanan Liu, Jing Wang, Minzhen Cai, Sen Liu, Pengtao Ma, Jingping Wang, Jingyang Niu

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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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Ru 金属配体参与构建 POM@MOF 以增强可见光诱导的拜尔-维利格氧化反应

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.