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Femtosecond Raman-Induced Kerr Effect Study of Temperature-Dependent Intermolecular Dynamics in Pyrrolidinium-Based Ionic Liquids: Effects of Anion Species

Cite this: J. Phys. Chem. B 2019, 123, 6, 1307–1323
Publication Date (Web):January 23, 2019
Copyright © 2019 American Chemical Society

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    We investigated the temperature dependence of the intermolecular vibrational dynamics of pyrrolidinium-based ionic liquids (ILs) with 10 different anion species using femtosecond Raman-induced Kerr effect spectroscopy. The features of the temperature-dependent vibrational spectra vary with the different anions. In the case of the ILs with spherical top anions, such as tetrafluoroborate and hexafluorophosphate, and trifluoromethanesulfonate, the spectral intensity in the low-frequency region below 50 cm–1 increases with rising temperature, while that in the high-frequency region above 50 cm–1 remains almost unchanged. Similar temperature-dependent features were also found in the bis(fluorosulfonyl)amide and bis(perfluoroalkylsulfonyl)amide salts. However, the difference spectra at respective temperature relative to 293 K indicate that the spectra of the bis(fluorosulfonyl)amide and bis(perfluoroalkylsulfonyl)amide salts are more temperature-sensitive in the low-frequency region below 50 cm–1 compared to those of the tetrafluoroborate, hexafluorophosphate, and trifluoromethanesulfonate salts. The spectra of 1-butyl-1-methylpyrrolidinium-based ILs with dicyanamide and tricyanomethide anions show a characteristic temperature dependence; in addition to an increase of the spectral intensity in the low-frequency region below 50 cm–1, a red shift of the spectra in the high-frequency side above 50 cm–1 was observed with increasing temperature. This implies that the librational motions of planar dicyanamide and tricyanomethide anions contribute substantially to the low-frequency spectra. We also compared the temperature-dependent low-frequency spectra of 1-butyl-1-methylpyrrolidinium- and 1-(2-methoxyethyl)-1-methylpyrrolidinium-based ILs with some anions. Although the spectral shapes are slightly different in the range of 70–150 cm–1, which can be attributed to the intramolecular vibrational modes of the cations, the temperature dependence of the spectral shapes is quite similar, indicating that the ether substitution in the cation side groups has little effects on the temperature dependence of the low-frequency spectra. The fragilities of the ILs were also estimated from the temperature-dependent viscosities and the glass-transition temperatures. The fragility parameter seems to be correlated with the temperature dependence of the first moment of the low-frequency spectral bands mainly arising from the intermolecular vibrations of the ILs.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcb.8b10269.

    • Synthetic procedures of the sample ILs; water contents of the ILs; temperature-dependent viscosity data of the ILs; atomic coordinates for the optimized pyrrolidinium cations at the B3LYP/6-311++G(d,p) level of theory; temperature-dependent Kerr transients, spectra, and difference spectra; lists of fit parameters for the Kerr transients and the Kerr spectra of the ILs; temperature dependence of the Bose–Einstein thermal occupation factor; and the complete author list of ref (45) (PDF)

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    Cited By

    This article is cited by 13 publications.

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    2. Markéta Havlová, Vladimír Dohnal. Phase Equilibria, Thermodynamic Behavior, and Transport Properties of Aqueous Solutions of [BMPYR] Trifluoromethanesulfonate and [BMPYR] Tricyanomethanide. Journal of Chemical & Engineering Data 2022, 67 (9) , 2108-2127.
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    10. Julia Leier, Nadine C. Michenfelder, Andreas‐Neil Unterreiner. Understanding the Photoexcitation of Room Temperature Ionic Liquids. ChemistryOpen 2021, 10 (2) , 72-82.
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