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

Andrew A Mariotti, Jingli Xie, Brendan Francis Abrahams, Alan Maxwell Bond, Anthony Gordon Wedd

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27 Citations (Scopus)

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.
Original languageEnglish
Pages (from-to)2530 - 2540
Number of pages11
JournalInorganic Chemistry
Volume46
Issue number7
DOIs
Publication statusPublished - 2007

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