Europium(III) and Its Halides in Anhydrous Room-Temperature Imidazolium-Based Ionic Liquids: A Combined TRES, EXAFS, and Molecular Dynamics Study

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Abstract
Combining spectroscopic techniques (TRES and EXAFS) and molecular dynamics simulations, we have investigated the state of trivalent europium dissolved in room-temperature ionic liquids (RTILs), as a function of the RTIL anion and in the presence of added chloride anions. The studied RTILs are based on the 1-butyl-3-methyl-imidazolium (Bumim+) cation and differ by their anionic counterparts: BF4-, PF6-, Tf- (triflate, CF3SO3-), and Tf2N- [(CF3SO2)2N -]. The results show the strong influence of the RTIL nature on the first solvation shell of europium and on its complexation with chloride. Depending on the RTIL, europium(III), which was introduced in solution as a triflate salt, is found to be solvated either by RTIL anions only or as neutral undissociated EuTf3 moieties completed by solvent anions. Kinetic effects, related to the viscosity of the RTIL and the nature of the europium salt, also markedly influence the coordination of added Cl- or F- anions to the metal.