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Inorg Chem. 2007 Apr 2;46(7):2530-40. Epub 2007 Mar 9.

Synthesis and voltammetry of [bmim]4[alpha-S2W18O62] and related compounds: rapid precipitation and dissolution of reduced surface films.

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  • 1School of Chemistry, The University of Melbourne, 3010 Victoria, Australia.

Abstract

1-n-Butyl-3-methylimidazolium (bmim) salts of [alpha-SiM12O40]4- and [alpha-S2M18O62]4- (M = Mo, W) were synthesized and characterized. In sharp contrast to the multiple one-electron diffusion-controlled reduction processes expected in solution at a glassy carbon electrode, reduction of these salts beyond the one-electron level in CH3CN (0.1 M [bmim][PF6]) led to rapid precipitation of arrays of microdroplets or microcrystals onto the surface. Upon oxidation these arrays dissolved on the electrochemical time scale, resulting in voltammograms displaying both diffusion-controlled and surface-confined behavior. These novel observations appear to be related to the ability of the [bmim]+ cations and polyoxometalate anions to form ion clusters in solution and to the lower solubilities of the reduced salts.

PMID:
17346039
[PubMed - indexed for MEDLINE]
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