Electrochemical properties of the [SiW10O36(M2O2E2)]6− polyoxometalate series (M = Mo(V) or W(V); E = S or O)

This paper deals with the electrochemical studies performed in DMF on three iso-electronic compounds of general formula γ-[SiW10O36(M2O2E2)]6−, which differ either with respect to the nature of their metallic centers (M = Mo(V) or W(V)) or the nature of the bridges between the Mo(V) atoms (E = O2− or S2−). Interestingly, cyclic voltammetry experiments performed in dry DMF revealed electrochemical processes both in oxidation and reduction modes. The nature of these processes is studied and elucidated by various electrochemical techniques such as coulometry, rotating disk voltammetry, spectro-electrochemistry (IR and UV-Vis), and NMR and DFT calculations.