Nockemann Peter, Servaes Kelly, Van Deun Rik, Van Hecke Kristof, Van Meervelt Luc, Binnemans Koen, Görller-Walrand Christiane
Katholieke Universiteit Leuven, Department of Chemistry, Celestijnenlaan 200F bus 2404, B-3001, Leuven, Belgium.
Inorg Chem. 2007 Dec 24;46(26):11335-44. doi: 10.1021/ic701752j. Epub 2007 Nov 29.
Uranyl complexes dissolved in room-temperature ionic liquids have diagnostic absorption and emission spectra which reflect the molecular symmetry and geometry. In particular, the characteristic vibrational fine structure of the absorption spectra allows identification of the molecular symmetry of a uranyl complex. The concept of speciation of uranyl complexes is illustrated for the hydrated uranyl ion, the tetrachloro complex [UO2Cl4]2-, the trinitrato complex [UO2(NO3)3]-, the triacetato complex [UO2(CH3COO)3]-, and the crown ether complex [UO2(18-crown-6)]2+ in imidazolium and pyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquids. The competition between 18-crown-6 and small inorganic ligands for coordination to the uranyl ion was investigated. The crystal structures of the hydrolysis product [(UO2)2(mu2-OH)2(H2O)6] UO2Br44 and imidazolium salt [C6mim]2[UO2Br4] are described.
溶解在室温离子液体中的铀酰配合物具有诊断性的吸收和发射光谱，这些光谱反映了分子的对称性和几何形状。特别是，吸收光谱的特征振动精细结构能够确定铀酰配合物的分子对称性。文中以水合铀酰离子、四氯配合物[UO₂Cl₄]²⁻、三硝酸根配合物[UO₂(NO₃)₃]⁻、三乙酸根配合物[UO₂(CH₃COO)₃]⁻以及咪唑鎓和吡咯烷鎓双（三氟甲基磺酰）亚胺离子液体中的冠醚配合物[UO₂(18-冠-6)]²⁺为例，阐述了铀酰配合物的形态概念。研究了18-冠-6与小的无机配体之间对铀酰离子配位的竞争。描述了水解产物[(UO₂)₂(μ₂-OH)₂(H₂O)₆]UO₂Br₄₄和咪唑鎓盐[C₆mim]₂[UO₂Br₄]的晶体结构。
