Abstract
Abstract The first and second redox potentials ( and ) of Keggin-type heteropolytungstate anions (α-[PW12O40]3− and α-[SiW12O40]4−) have been determined in various solvents by means of cyclic voltammetry. The difference () between and , being theoretically associated with the solvation energies of the polyanions, does not correlate with the permittivity of the solvent, in conflict with an expectation based on the Born-type electrostatic solvation model. In contrast, has been found to show some definite correlations with such empirical solvent parameters as acceptor numbers. This shows that the short-range interactions (i.e., donor–acceptor effects or hydrogen bonds) between the heteropolyanion and its primary solvents play the most significant role in the solvation of the heteropolyanions. We have thus proposed a new analytical equation for evaluating the short-range ion–solvent interaction energy.
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