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岡村 浩之; 坂江 広基*; 木谷 径治*; 平山 直紀*; 青柳 登; 斎藤 拓巳*; 下条 晃司郎; 長縄 弘親; 井村 久則*
Polyhedron, 31(1), p.748 - 753, 2012/01
被引用回数:28 パーセンタイル:87.66(Chemistry, Inorganic & Nuclear)The extraction constant and the two-phase stability constant of tris(2-thenoyltrifluoroacetonato) europium(III) between 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([Cmim][TfN]) as an ionic liquid and an aqueous phase were determined by considering the extraction equilibria. Specific solute-solvent interactions between the neutral Eu(III) chelate and [Cmim][TfN] molecules were revealed from the relationships between the distribution constant of the enol form of 2-thenoyltrifluoroacetone (Htta) and the distribution constant () of the neutral Eu(III) chelate. The coordination environment of Eu in the neutral Eu(III) chelate in [Cmim][TfN] was investigated by time-resolved laser-induced fluorescence spectroscopy and infrared absorption spectroscopy. Both methods consistently indicated that not only the Eu(III)chelate extracted but also Eu(tta)(HO) synthesized as a solid crystal were almost completely dehydrated in [Cmim][TfN] saturated with water. Consequently, the higher or extractability of the neutral Eu(III) chelate in the [Cmim][TfN] system can be ascribed to the dehydration of the Eu(III) chelate, which is caused by the specific solvation with [Cmim][TfN] molecules.
岡村 浩之; 坂江 広基*; 木谷 径治*; 平山 直紀*; 下条 晃司郎; 長縄 弘親; 井村 久則*
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Solvation of a central Eu(III) ion in the tris(2-thenoyltrifluoroacetonato)europium(III) (Eu(tta)) chelate in 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([Cmim][TfN]; = 2-10) was investigated by time-resolved laser-induced fluorescence spectroscopy and infrared absorption spectroscopy. Both spectroscopic studies consistently indicated that Eu(tta) extracted or synthesized was almost completely dehydrated in [Cmim][TfN] saturated with water. Furthermore, it was found that a small amount of [Cmim][TfN] caused the dehydration of the Eu(III) chelate in 1,2-dichloroethane. The release of the water molecules from the Eu(III) inner coordination sphere of Eu(tta) can be ascribed to the specific solvation of [Cmim][TfN], i.e., coordination of TfN molecules.