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Synthesis, Structural and Electrochemical Properties of the [Sb^III₂SiMo₁₂O₄₀]^4– anion, a Bicapped Keggin Polyoxometalate

Lookup NU author(s): Dr John ErringtonORCiD

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Abstract

The [Sb₂SiMo₁₂O₄₀]^4– anion has been synthesized as its ammonium salt, which was obtained as pure crystals in high yield under controllable conditions. The structure of the six-electron reduced di-antimony capped Keggin compound (NH₄)₄[Sb₂SiMo₁₂O₄₀].11H₂O has been determined by single-crystal X-ray diffraction and shows two capping groups grafted onto the reduced {SiMo₁₂O₄₀} central core. A 2D solid network results from interactions between the outer Sb caps and oxygen atoms of POM neighbors. The delocalization of six electrons over the 12 Mo centers modifies both the IR and UV–visible spectra. The bicapped polyoxometalate (POM) exhibits two quasi-reversible multi-electron transfers in the range 0.0 to 0.3 V/SCE in aqueous solution. A mechanism is proposed for the reversible oxidation process which involves concerted Mo^V/Mo^VI redox couples with concomitant hydrolysis of the two outer Sb(III) capping groups.

Publication metadata

Author(s): Canioni R, Cadot E, Errington RJ, Leclerc-Laronze N, Roche-Marchal C

Publication type: Article

Publication status: Published

Journal: Current Inorganic Chemistry

Year: 2017

Volume: 7

Issue: 1

Pages: 13-20

Online publication date: 27/11/2017

Acceptance date: 14/10/2017

ISSN (print): 1877-9441

ISSN (electronic): 1877-945X

Publisher: Bentham Science

URL: https://doi.org/10.2174/1877944107666171102160358

DOI: 10.2174/1877944107666171102160358

Notes: Submitted as an article for a Special Issue: Clusters, Polyoxometalates and Metal-Organic Frameworks: from synthesis to applications Guest Editor(s): Sébastien Floquet, Nathalie Audebrand, Rosa Llusar, Maksim Sokolov

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