Effects of Aromaticity in Cations and Their Functional Groups on the Low-Frequency Spectra and Physical Properties of Ionic Liquids
Abstract
We investigate the temperature dependence of low-frequency spectra in the frequency range of 0.3–200 cm-1 for ionic liquids (ILs) whose cations possess two systematically different cyclic groups, using femtosecond Raman-induced Kerr effect spectroscopy. The target ILs are bis(trifluoromethylsulfonyl)amide [NTf2]– salts of 1-cyclohexylmethyl-1-methylpyrrolidinium [CHxmMPyrr]+, 1-cyclohexylmethyl-3-methylimidazolium [CHxmMIm]+, N-cyclohexylmethylpyridinium [CHxmPy]+, 1-benzyl-1-methylpyrrolidinium [BzMPyrr]+, 1-benzyl-3-methylimidazolium [BzMIm]+, and N-benzylpyridinium [BzPy]+ cations. The aim of this study is to better understand the effects of aromaticity in the cations’ constituent groups on the temperature-dependent low-frequency spectral features of the ILs. The low-frequency spectra of these ILs are temperature dependent, but the temperature-dependent spectrum of [CHxmMPyrr][NTf2] is different from that of other ILs. While [CHxmMPyrr][NTf2] shows spectral changes with temperature in the low-frequency region below 50 cm-1, the other ILs also show spectral changes in the high-frequency region above 80 cm-1 (above 50 cm-1 in the case of [BzMPyrr][NTf2]). We conclude that the spectral change in the low-frequency region is due to both the cation and anion, while the change in the high-frequency region is attributed to the red shift of the aromatic ring librations. On the basis of the plots of the first moment of the spectra vs. temperature, we found that the first moment of the low-frequencymore »
- Authors:
-
- Chiba Univ. (Japan). Dept. of Nanomaterial Science
- Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept.
- Chiba Univ. (Japan). Dept. of Chemistry
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1425020
- Report Number(s):
- BNL-200000-2018-JAAM
Journal ID: ISSN 1520-6106; TRN: US1802003
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
- Additional Journal Information:
- Journal Volume: 119; Journal Issue: 29; Journal ID: ISSN 1520-6106
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ionic; liquids
Citation Formats
Kakinuma, Shohei, Ramati, Sharon, Wishart, James F., and Shirota, Hideaki. Effects of Aromaticity in Cations and Their Functional Groups on the Low-Frequency Spectra and Physical Properties of Ionic Liquids. United States: N. p., 2014.
Web. doi:10.1021/jp509412z.
Kakinuma, Shohei, Ramati, Sharon, Wishart, James F., & Shirota, Hideaki. Effects of Aromaticity in Cations and Their Functional Groups on the Low-Frequency Spectra and Physical Properties of Ionic Liquids. United States. https://doi.org/10.1021/jp509412z
Kakinuma, Shohei, Ramati, Sharon, Wishart, James F., and Shirota, Hideaki. Mon .
"Effects of Aromaticity in Cations and Their Functional Groups on the Low-Frequency Spectra and Physical Properties of Ionic Liquids". United States. https://doi.org/10.1021/jp509412z. https://www.osti.gov/servlets/purl/1425020.
@article{osti_1425020,
title = {Effects of Aromaticity in Cations and Their Functional Groups on the Low-Frequency Spectra and Physical Properties of Ionic Liquids},
author = {Kakinuma, Shohei and Ramati, Sharon and Wishart, James F. and Shirota, Hideaki},
abstractNote = {We investigate the temperature dependence of low-frequency spectra in the frequency range of 0.3–200 cm-1 for ionic liquids (ILs) whose cations possess two systematically different cyclic groups, using femtosecond Raman-induced Kerr effect spectroscopy. The target ILs are bis(trifluoromethylsulfonyl)amide [NTf2]– salts of 1-cyclohexylmethyl-1-methylpyrrolidinium [CHxmMPyrr]+, 1-cyclohexylmethyl-3-methylimidazolium [CHxmMIm]+, N-cyclohexylmethylpyridinium [CHxmPy]+, 1-benzyl-1-methylpyrrolidinium [BzMPyrr]+, 1-benzyl-3-methylimidazolium [BzMIm]+, and N-benzylpyridinium [BzPy]+ cations. The aim of this study is to better understand the effects of aromaticity in the cations’ constituent groups on the temperature-dependent low-frequency spectral features of the ILs. The low-frequency spectra of these ILs are temperature dependent, but the temperature-dependent spectrum of [CHxmMPyrr][NTf2] is different from that of other ILs. While [CHxmMPyrr][NTf2] shows spectral changes with temperature in the low-frequency region below 50 cm-1, the other ILs also show spectral changes in the high-frequency region above 80 cm-1 (above 50 cm-1 in the case of [BzMPyrr][NTf2]). We conclude that the spectral change in the low-frequency region is due to both the cation and anion, while the change in the high-frequency region is attributed to the red shift of the aromatic ring librations. On the basis of the plots of the first moment of the spectra vs. temperature, we found that the first moment of the low-frequency spectrum of the IL whose cation does not have an aromatic ring is less temperature dependent than that of the other ILs. However, the intrinsic first moment, the first moment at 0 K, of the low-frequency spectrum is governed by the absence or presence of a charged aromatic group, while a neutral aromatic group does not have much influence on determining the intrinsic first moment.},
doi = {10.1021/jp509412z},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 29,
volume = 119,
place = {United States},
year = {Mon Dec 01 00:00:00 EST 2014},
month = {Mon Dec 01 00:00:00 EST 2014}
}
Figures / Tables:
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