Cation effect on the electrochemical reduction of polyoxometalates in room temperature ionic liquids

Polyoxometalates (POMs) are compounds that undergo multiple successive one-electron redox transitions, making them convenient model reactants to study ion solvation effects. Room temperature ionic liquids (RTILs) are solvents made entirely of ions, and are expected to have interactions with the highly negatively charged POM reduction products. In this work, 12 RTILs with a range of different anions ([FSI](-)=bis(fluorosulfonyl)imide, [TFSI](-)=bis(trifluoromethylsul-fonyl)imide, [BETI](-)=bis(pentafluoroethylsulfonyl)imide, [BF4](-), [PF6](-)) and cations (imidazolium, pyrrolidinium, sulfonium, ammonium, phosphonium) were employed as solvents to study the kinetics and thermodynamics of [S2W18O62](4-) reduction, to shed light on solvation effects and ion-pairing effects caused by different RTIL structures. Up to six reversible reduction processes (producing highly negatively charged [S2W18O62](10-)) were observed. For the RTILs that showed multiple processes, a clear trend in both the thermodynamics (inferred from the reduction peak potentials) and kinetics (inferred from the peak-to-peak separation) was observed, in the order: imidazolium < sulfonium asymptotic to ammonium < pyrrolidinium < phosphonium, supporting strong interac-tions of the negatively charged POM reduction products with the cation. Two related POMs, [P2W18O62](6-) and [PW12O40](3-), were also studied in the optimum RTIL found for [S2W18O62](4-) ([C2mim][FSI]=1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide), revealing fast kinetics and asymmetric peaks for [PW12O40](3-). This work demonstrates the importance of understanding the solvation effects of RTIL ions for highly charged electrogenerated products, allowing tuning of the RTIL structure to achieve the optimum kinetics and thermodynamics for an electrochemical process.