Gaillard Clotilde, Billard Isabelle, Chaumont Alain, Mekki Soufiane, Ouadi Ali, Denecke Melissa A, Moutiers Gilles, Wipff Georges
Institut de Recherches Subatomiques, CNRS-IN2P3, B.P. 28, 67037 Strasbourg Cedex 2, France.
Inorg Chem. 2005 Nov 14;44(23):8355-67. doi: 10.1021/ic051055a.
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.
结合光谱技术（TRES和EXAFS）以及分子动力学模拟，我们研究了溶解在室温离子液体（RTILs）中的三价铕的状态，该状态是室温离子液体阴离子的函数，并考察了添加氯离子时的情况。所研究的室温离子液体基于1-丁基-3-甲基咪唑鎓（Bumim⁺）阳离子，其阴离子部分不同：BF₄⁻、PF₆⁻、Tf⁻（三氟甲磺酸盐，CF₃SO₃⁻）和Tf₂N⁻[（CF₃SO₂）₂N⁻]。结果表明室温离子液体的性质对铕的第一溶剂化层及其与氯的络合有强烈影响。根据室温离子液体的不同，以三氟甲磺酸盐形式引入溶液中的铕（III），被发现要么仅被室温离子液体阴离子溶剂化，要么以由溶剂阴离子补充的中性未解离EuTf₃部分的形式存在。与室温离子液体的粘度和铕盐的性质相关的动力学效应，也显著影响添加的Cl⁻或F⁻阴离子与金属的配位。
