The selection of an appropriate solvent is essential for achieving high yields and selectivity in chemical reactions. The chemical and physical parameters of organic solvents have been classified into several groups, and solvents can be compared with each other with respect to these properties. The acceptor number (AN), donor number (DN) and polarity (ET N) have been widely accepted and used for theoretically and quantitatively evaluating the properties of organic solvents. In a similar manner, the AN, DN and ET N of room temperature ionic liquids (RTILs) have been estimated from spectral changes in solvatochromic compounds. In this paper, the AN and ET N of eight types of imidazolium-based RTILs were estimated from the relationship between the AN and ET N values and the first redox potential obtained from the voltammograms of polyoxometalates (POMs) in various organic solvents. The obtained parameters were compared with those estimated by spectrophotometric methods reported previously by several groups. This new method for estimating the AN and ET N of RTILs using the voltammetric behaviour of POMs with low charge density and high symmetry could provide the other path to obtain more reliable AN and ET N of RTILs.
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