Abstract
In situ solidification of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIM][TFSI]) from melt has been investigated by using a diamond anvil cell under pressures up to about 6.0 GPa at room temperature. The results indicate that non-monotonic pressure induced Raman shifts and variation of the full width at half-maximum are suggestive of a phase transition at about 1.8 GPa upon compression, which was further confirmed to be a phase transition from liquid to a superpressurized glass by line broadening measurements of the sharp R 1 ruby fluorescence line and synchrotron X-ray diffraction measurements. The conformational changes of C 1 and C 2 conformers of the [TFSI] anion under high pressure are discussed; the C 2 conformers are predominant under high pressures. In addition, the Raman spectra of [BMIM][TFSI] under different conditions are compared in detail. The results show that the structure of the glassy state at low temperature is different from that of the high pressure state, while the glassy state is mainly composed of C 2 anion conformers, which is similar to the high pressure state.
Similar content being viewed by others
References
Welton, T.: Room-temperature ionic liquids. Solvents for synthesis and catalysis. Chem. Rev. 99, 2071–2084 (1999)
Huddleston, J.G., Rogers, R.D.: Room temperature ionic liquids as novel media for clean liquid–liquid extraction. Chem. Commun. 16, 1765–1766 (1998)
Buzzeo, M.C., Evans, R.G., Compton, R.G.: Non-haloaluminate room-temperature ionic liquids in electrochemistry—a review. Chem. Phys. Chem. 5, 1106–1120 (2004)
Rantwijk, F.V., Madeira, L.R., Sheldon, R.A.: Biocatalytic transformations in ionic liquids. Trends in Biotechnol. 21, 131–138 (2003)
Armstrong, D.W., Zhang, L.K., He, L., Gross, M.L.: Ionic liquids as matrixes for matrix-assisted laser desorption/ionization mass spectrometry. Anal. Chem. 73, 3679–3686 (2001)
Wang, P., Zakeeruddin, S.M., Moser, J.E., Gratzel, M.: A new ionic liquid electrolyte enhances the conversion efficiency of dye-sensitized solar cells. J. Phys. Chem. B 107, 13280–13285 (2003)
Itoh, H., Naka, K., Chujo, Y.: Synthesis of gold nanoparticles modified with ionic liquid based on the Iimidazolium cation. J. Am. Chem. Soc. 126, 3026–3027 (2004)
Buzzeo, M.C., Hardacre, C., Compton, R.G.: Use of room temperature ionic liquids in gas sensor design. Anal. Chem. 76, 4583–4588 (2004)
Russina, O., Fazio, B., Schmidt, C., Triolo, A.: Structural organization and phase behaviour of 1-butyl-3-methylimidazolium hexafluorophosphate: an high pressure Raman spectroscopy study. Phys. Chem. Chem. Phys. 13, 12067–12074 (2011)
Saouane, S., Norman, S.E., Hardacre, C., Fabbiani, F.P.A.: Pinning down the solid-state polymorphism of the ionic liquid [BMIM][PF6]. Chem. Sci. 4, 1270–1280 (2013)
Imai, Y., Takekiyo, T., Abe, H., Yoshimura, Y.: Pressure- and temperature-induced Raman spectral changes of 1-butyl-3-methylimidazolium tetrafluoroborate. High Press Res. 31, 53–57 (2011)
Yoshimura, Y., Takekiyo, T., Imai, Y., Abe, H.: Pressure-induced spectral changes of room-temperature ionic liquid, N,N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium bis(trifluoromethylsulfonyl)imide, [DEME][TFSI]. J. Phys. Chem. C 116, 2097–2101 (2012)
Su, L., Li, L.B., Hu, Y., Yuan, C.S., Shao, C.G., Hong, S.M.: Phase transition of [CnMIM][PF6] under high pressure up to 1.0 GPa. J. Chem. Phys. 130, 184503–184504 (2009)
Su, L., Li, M., Zhu, X., Wang, Z., Chen, Z.P., Li, F.F., Zhou, Q., Hong, S.M.: In situ crystallization of low-melting ionic liquid [BMIM] [PF6] under high pressure up to 2 GPa. J. Phys. Chem. B 114, 5061–5065 (2010)
Su, L., Zhu, X., Wang, Z., Cheng, X.R., Wang, Y.Q., Yuan, C.S., Chen, Z.P., Ma, C.L., Li, F.F., Zhou, Q., Cui, Q.L.: In situ observation of multiple phase transitions in Ll-melting ionic liquid [BMIM][BF4] under high pressure up to 30 GPa. J. Phys. Chem. B 116, 2216–2222 (2012)
Li, H.N., Zhang, Y.Q., Zhu, X., Cheng, X.R., Shao, C.G., Wu, J., Li, J.Y., Ren, Y.F., Wang, Z., Wang, Y.Q., Yuan, C.S., Su, L.: In situ solidification of ionic liquid [EMIM][EtOSO3] from melt under high pressure. High Press Res. 4, 751–759 (2013)
Shigemi, M., Takekiyo, T., Abe, H., Hamaya, N., Yoshimura, Y.: Pressure-induced solidification of 1-butyl-3-methylimidazolium tetrafluoroborate. J. Solution Chem. 43, 1614–1624 (2014)
Mudring, A.V.: Solidification of ionic liquids: theory and techniques. Aust. J. Chem. 63, 544–564 (2010)
Mao, H.K., Bell, P.M., Shaner, J.W., Steinberg, D.J.: Specific volume measurements of Cu, Mo, Pd, and Ag and calibration of the ruby R1 fluorescence pressure gauge from 0.06 to 1 Mbar. Appl. Phys. 49, 3276–3283 (1978)
Hammersley, A.P., Svensson, S.O., Hanfland, M., Fitch, A.N., Hausermann, D.: Two-dimensional detector software: from real detector to idealised image or two-theta scan. High Press Res. 14, 235–248 (1996)
Berg, R.W., Deetlefs, M., Seddon, K.R., Shim, I., Thompson, J.M.: Raman and ab initio studies of simple and binary 1-alkyl-3-methylimidazolium ionic liquids. J. Phys. Chem. B 109, 19018–19025 (2005)
Castriota, M., Caruso, T., Agostino, R.G., Cazzanelli, E., Henderson, W.A., Passerin, S.: Raman investigation of the ionic liquid N-methyl-N-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide and its mixture with LiN(SO2CF3)2. J. Phys. Chem. A 109, 92–96 (2005)
Kiefer, J., Fries, J., Leipertz, A.: Experimental vibrational study of imidazolium-based ionic liquids: raman and infrared spectra of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide and 1-ethyl-3-methylimidazolium ethylsulfate. Applied Spectrosc. 12, 1306–1311 (2007)
Lassegues, J.C., Grondin, J., Holomb, R., Johansson, P.: Raman and ab initio study of the conformational isomerism in the 1-ethyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl) imide ionic liquid. J. Raman Spectrosc. 38, 551–558 (2007)
Chang, H.C., Jiang, J.C., Su, J.C., Chang, C.Y., Lin, S.H.: Evidence of rotational isomerism in 1-butyl-3-methylimidazolium halides: a combined high pressure infrared and Raman spectroscopic study. J. Phys. Chem. A 111, 9201–9206 (2007)
Piermarini, G.J., Block, S., Barnett, J.D.: Hydrostatic limits in liquids and solids to 100 kbar. J. Appl. Phys. 44, 5377–5382 (1973)
Ozawa, R., Hayashi, S., Saha, S., Kobayashi, A., Hamaguchi, H.: Rotational isomerism and structure of the 1-butyl-3-methylimidazolium cation in the ionic liquid state. Chem. Lett. 32, 948–949 (2003)
Fujii, K., Fujimori, T., Takamuku, T., Kanzaki, R., Umebayashi, Y., Ishiguro, S.: Conformational equilibrium of bis(trifluoromethanesulfonyl) imide anion of a room-temperature ionic liquid: Raman spectroscopic study and DFT calculations. J. Phys. Chem. B 110, 8179–8183 (2006)
Tokuda, H., Hayamizu, K., Ishii, K., Susan, M.A.B.H., Watanabe, M.: Physicochemical properties and structures of room temperature ionic liquids. 1. Variation of anionic species. J. Phys. Chem. B 108, 16593–16600 (2004)
Rivera, C.A., Kaminski, K., Leon, C., Paluch, M.: Ion dynamics under pressure in an ionic liquid. J. Phys. Chem. B 112, 3110–3114 (2008)
Scott, T.H.: Ionic Liquids-Classes. Properties, InTech, Rijeka, Croatia (2011)
Takatsugu, E., Sabyasachi, S.: Ionic dynamics in [C4mim]NTf2 in the glassy and liquid states: results from 13C and 1H NMR spectroscopy. J. Phys. Chem. B 118, 14888–14898 (2014)
Acknowledgments
This work is supported by the National Science Foundation of China (Nos. 21273206 and 31201377), as well as Key Research Project of Higher Education of Henan Province (No. 15A140016 and No. 2010GGJS-110).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Wu, J., Zhu, X., Li, H. et al. Combined Raman Scattering and X-ray Diffraction Study of Phase Transition of the Ionic Liquid [BMIM][TFSI] Under High Pressure. J Solution Chem 44, 2106–2116 (2015). https://doi.org/10.1007/s10953-015-0393-2
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10953-015-0393-2