期刊
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
卷 2022, 期 10, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejic.202200019
关键词
Electrochemistry; Hybrid materials; Mixed-metal clusters; Polyoxometalates; Spectroelectrochemistry
资金
- EPSRC through the Centre for Doctoral Training in Sustainable Chemistry [EP/L015633/1]
- University of Nottingham Propulsion Futures Beacon of Excellence
- Leverhulme Trust [RPG-2016-442]
- EPSRC
- EPSRC [EP/L015633/1] Funding Source: UKRI
A mixed-addenda polyoxometalate cluster containing both W and Mo centers was synthesized under acidic conditions. The structure and electronic effects of metal substitution were studied and compared to its tungsten-only analogue.
A mixed-addenda W/Mo hybrid polyoxometalate cluster - K-6[P2W15Mo2O61(POC6H5)(2)] (1) was synthesised from the condensation of K-10[P2W15Mo2O61] and PO3C6H7 under acidic conditions. Single-crystal X-ray diffraction confirmed the structure of the hybrid cluster and the presence of two Mo centres in the cap of the lacunary cluster. The electronic effects of metal substitution were studied by cyclic voltammetry, spectroelectrochemistry and electron paramagnetic resonance spectroscopy and supported by density functional theory calculations. Comparing 1 to its tungsten-only analogue K-6[P2W17O61(POC6H5)(2)] (2), a more positive potential for the first reduction process was induced by the substitution of W for Mo, consistent with a significant lowering of the cluster LUMO energy.
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