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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 |
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| Authors: | Hiroyuki Okamura Hiroki SakaeKeiji Kidani Naoki HirayamaNoboru Aoyagi Takumi SaitoKojiro Shimojo Hirochika NaganawaHisanori Imura |
| Institution: | a Division of Material Sciences, Graduate School of Natural Science and Technology, Kanazawa University, Kakuma, Kanazawa 920-1192, Japan b Division of Environment and Radiation Sciences, Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195, Japan c Division of Material Chemistry, Graduate School of Natural Science and Technology, Kanazawa University, Kakuma, Kanazawa 920-1192, Japan d Department of Chemistry, Faculty of Science, Toho University, Miyama 2-2-1, Funabashi 274-8510, Japan e Department of Nuclear Engineering and Management, School of Engineering, The University of Tokyo, 7-3-1 Bunkyo-ku, Tokyo 113-8656, Japan |
| Abstract: | The extraction constant and the two-phase stability constant (KD,Mβ3) of tris(2-thenoyltrifluoroacetonato)europium(III) between 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (C4mim]Tf2N]) as an ionic liquid and an aqueous phase were determined by considering the extraction equilibria including anionic tetrakis(2-thenoyltrifluoroacetonato)europate(III). Specific solute-solvent interactions between the neutral Eu(III) chelate and C4mim]Tf2N] molecules were revealed from the relationships between the distribution constant of the enol form of 2-thenoyltrifluoroacetone (Htta) as a proton chelate and the distribution constant (KD,M) of the neutral Eu(III) chelate because the C4mim]Tf2N] system gave the high KD,Mβ3 value compared with those in conventional molecular solvents such as benzene and 1,2-dichloroethane. The coordination environment of Eu3+ in the neutral Eu(III) chelate in C4mim]Tf2N] 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(H2O)3 synthesized as a solid crystal were almost completely dehydrated in C4mim]Tf2N] saturated with water. Consequently, the higher KD,M or extractability of the neutral Eu(III) chelate in the C4mim]Tf2N] system can be ascribed to the dehydration of the Eu(III) chelate, which is caused by the specific solvation with C4mim]Tf2N] molecules. |
| Keywords: | Ionic liquids Europium(III) chelate Time-resolved laser-induced fluorescence spectroscopy IR absorption spectroscopy Solvation 1-(2-Thienyl)-4 4 4-trifluoro-1 3-butanedione |
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