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論文

Laser-induced fluorescence and infrared spectroscopic studies on the specific solvation of tris(1-(2-thienyl)-4,4,4-trifluoro-1,3-butanedionato)europium(III) in an ionic liquid

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

https://doi.org/10.1016/j.poly.2011.10.031

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 ([C $_{4}$ mim][Tf $_{2}$ N]) 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 [C $_{4}$ mim][Tf $_{2}$ N] molecules were revealed from the relationships between the distribution constant of the enol form of 2-thenoyltrifluoroacetone (Htta) and the distribution constant ( $_{rm D,M}$ ) of the neutral Eu(III) chelate. The coordination environment of Eu $^{3+}$ in the neutral Eu(III) chelate in [C $_{4}$ mim][Tf $_{2}$ N] 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) $_{3}$ (H $_{2}$ O) $_{3}$ synthesized as a solid crystal were almost completely dehydrated in [C $_{4}$ mim][Tf $_{2}$ N] saturated with water. Consequently, the higher $_{rm D,M}$ or extractability of the neutral Eu(III) chelate in the [C $_{4}$ mim][Tf $_{2}$ N] system can be ascribed to the dehydration of the Eu(III) chelate, which is caused by the specific solvation with [C $_{4}$ mim][Tf $_{2}$ N] molecules.

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イオン液体中におけるユウロピウム(III)キレートの溶媒和に関する分光学的研究

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*

no journal, ,

Solvation of a central Eu(III) ion in the tris(2-thenoyltrifluoroacetonato)europium(III) (Eu(tta) $_{3}$ ) chelate in 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C $_{n}$ mim][Tf $_{2}$ N]; = 2-10) was investigated by time-resolved laser-induced fluorescence spectroscopy and infrared absorption spectroscopy. Both spectroscopic studies consistently indicated that Eu(tta) $_{3}$ extracted or synthesized was almost completely dehydrated in [C $_{n}$ mim][Tf $_{2}$ N] saturated with water. Furthermore, it was found that a small amount of [C $_{4}$ mim][Tf $_{2}$ N] 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) $_{3}$ can be ascribed to the specific solvation of [C $_{n}$ mim][Tf $_{2}$ N], i.e., coordination of Tf $_{2}$ N $^{-}$ molecules.