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Intensifying Photocatalytic Baeyer–Villiger Oxidation of Ketones with the Introduction of Ru Metalloligands and Bimetallic Units in POM@MOF
- Source :
- Inorganic Chemistry; April 2024, Vol. 63 Issue: 16 p7325-7333, 9p
- Publication Year :
- 2024
-
Abstract
- The synthesis of visible light-responsive and efficient photocatalysts toward green Baeyer–Villiger oxidation organic synthesis is of extraordinary significance. In this work, we have synthesized two examples of visible light responsive crystalline polyoxometalate@metal–organic framework materials Ru-NiMoand Ru-CoMoby introducing Ru metalloligands and {CdM3O12} bimetallic units (M = Ni or Co). This is the first report of metalloligand-modified polyoxometalate@metal–organic framework materials with bimetallic nodes, and the materials form a three-dimensional framework directly through coordination bonds between {CdM3O12} bimetallic units and metalloligands. In particular, Ru-NiMocan achieve efficient photocatalytic conversion of cyclohexanone to ε-caprolactone in yields as high as 95.5% under visible light excitation in the range of λ > 400 nm, achieving a turnover number and turnover frequency of 955 and 440 h–1, respectively, which are the best known photocatalysts for Baeyer–Villiger oxidation, while apparent quantum yield measured at 485 nm is 4.4%. Moreover, Ru-NiMoexhibited excellent structural stability and recyclability, producing a 90.8% yield after five cycles of recycling.
Details
- Language :
- English
- ISSN :
- 00201669 and 1520510X
- Volume :
- 63
- Issue :
- 16
- Database :
- Supplemental Index
- Journal :
- Inorganic Chemistry
- Publication Type :
- Periodical
- Accession number :
- ejs66046577
- Full Text :
- https://doi.org/10.1021/acs.inorgchem.4c00217