in Figure . It was found that little oxidation and reduction behavior occurred despite the increase solubility of the POM versus SMT. FTIR data, shown in the same figure, shows little to no complexing of the POM with species in solution while SMT shows some degree of complexing, as discussed previously. It has been found that silicotungstic acid shows two electron reduction and oxidation in 0.1M HCl. The difference between the system found in literature and the current study is both the solvent (DMF versus water), and the ionic strength of the solution (H + has less interaction with the POM than Li + ) as well as the presence of Gd 3+ might limit electrochemical reactions of the POM. The current study examined the electrochemistry of gadolinium-POM complexes in concentrated LiCl-DMF solutions. It was found that Gd 3+ and MT 3-electrostatically interacted rather than forming chemical bonds through the Ot group of the MT molecule. Electrochemically, it was found that Gd 3+ exhibited more reversible electrochemistry but the interaction of the two species allowed for an additional electron transfer to occur in the regime of Gd electrodeposition. Si based POMs did not show electrochemical behavior in the presence of Gd 3+ and showed virtually no electrostatic interaction between the POM and the cations in solution. The current work provides fundamental insight into the role of metallic and cationic species on the electrochemical behavior of lanthanide-POM complexes.