A Mixed‐Addenda Mo/W Organofunctionalised Hybrid Polyoxometalate

A mixed‐addenda W/Mo hybrid polyoxometalate cluster – K6[P2W15Mo2O61(POC6H5)2] (1) was synthesised from the condensation of K10[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 c...

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Bibliographic Details
Published in:European journal of inorganic chemistry 2022-04, Vol.2022 (10), p.n/a
Main Authors: Amin, Sharad S., Cameron, Jamie M., Winslow, Max, Davies, E. Stephen, Argent, Stephen P., Robinson, David, Newton, Graham N.
Format: Article
Language:English
Subjects:
Clusters
Crystal structure
Density functional theory
Electrochemistry
Electron paramagnetic resonance
Hybrid materials
Inorganic chemistry
Mixed-metal clusters
Polyoxometalates
Polyoxometallates
Spectroelectrochemistry
Substitutes
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Summary:A mixed‐addenda W/Mo hybrid polyoxometalate cluster – K6[P2W15Mo2O61(POC6H5)2] (1) was synthesised from the condensation of K10[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 K6[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. Substitution of metal addenda was explored as a method to modulate the electronic structure of organofunctionalised hybrid polyoxometalate clusters. Here we study the effects of Mo substitution into a W‐based cluster. Through a range of spectroscopic and electrochemical techniques, substitution of W for Mo was shown to significantly modify the frontier orbital energies of the hybrid cluster.
ISSN:1434-1948
1099-0682
DOI:10.1002/ejic.202200019