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Tools for studying ion solvation and ion pair formation in ionic liquids: isotopic substitution Raman spectroscopy

Analytical Sciences volume 38, pages 1025–1031 (2022)Cite this article

Abstract

Isotopic H/D or 6/7Li substitution Raman spectroscopy was applied to new kinds of ionic liquids; N-methylimidazole (C1Im) and acetic acid (CH3COOH) as the pseudo-protic ionic liquid (pPIL), and both of the neat and the 2,2,3,3-tetrafluoropropyl ether (HFE) diluted Li-glyme solvate ionic liquids (SIL) [Li(Gn)][TFSA] (Gn, glyme n = 3 or 4); TFSA, bis(trifluoromethanesulfonyl)amide) to clarify the proton transfer or the Li+ solvation/ion pair formation. The isotopic substitution Raman (ISR) spectra were obtained as the difference between the samples containing the same composition except the substituted isotope. The calculated and theoretical ISR spectra were also evaluated for comparison. With the C1Im–CH3COOH(D) pPIL, the Raman bands attributable to the C1Im/C1HIm+ gave signals of differential shape, and they were well reproduced with the curve fitting by taking the small amount of C1HIm+ and CH3COO– generation into consideration. The ISR spectra for the SIL were well explained by the formation of the Li–TFSA contact ion pair (CIP) and the solvent shared ion pair (SSIP) in the [Li(G3)][TFSA] SIL. In addition, the ISR spectra for the HFE-diluted [Li(G4)][TFSA] SIL clearly proved that the HFE hardly coordinates to the Li+ in the HFE-diluted SIL. Here, the ISR spectroscopy is proposed as a new tool for studying the ion solvation and the ion pair formation in ionic liquids.

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Acknowledgements

This study was supported in part by Grants-in-Aid for Scientific Research No.18H01994 and a Research Fellowship No.17J02361 from the Japan Society for the Promotion of Science (JSPS) and JST ALCA-SPRING Grant Number JPMJAL1301, Japan. Raman measurements were recorded at the center for coordination of research facilities in Niigata University.

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Authors and Affiliations

  1. Department of Pure and Applied Chemistry, Faculty of Science and Technology, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba, 278-8510, Japan

    Hikari Watanabe

  2. Graduate School of Science and Technology, Niigata University, 8050 Ikarashi, 2-no-cho, Nishi-ku, Niigata City, 950-2181, Japan

    Nana Arai, Jihae Han, Yui Kawana & Yasuhiro Umebayashi

  3. Japan Advanced Chemical Energy Research Center (ACERC), Institute of Advanced Science, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama, 240-8501, Japan

    Seiji Tsuzuki

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  1. Hikari Watanabe
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Correspondence to Yasuhiro Umebayashi.

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Watanabe, H., Arai, N., Han, J. et al. Tools for studying ion solvation and ion pair formation in ionic liquids: isotopic substitution Raman spectroscopy. ANAL. SCI. 38, 1025–1031 (2022). https://doi.org/10.1007/s44211-022-00121-7

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  • DOI: https://doi.org/10.1007/s44211-022-00121-7

Keywords

  • Isotopic substitution Raman spectroscopy
  • Ionic liquid
  • Inter-ionic interaction