Spectroscopic Assessment of Intra- and Intermolecular Hydrogen Bonding in Ether-Functionalized Imidazolium Ionic Liquids
Abstract
Functionalization of the imidazolium (Im+) cationic component of ionic liquids (ILs) with ether chains affords the possibility of tuning their properties through manipulation of the resulting interion and intramolecular interactions. Herein, we quantify these interactions at the molecular level through analysis of the vibrational spectra displayed by size-selected and cryogenically cooled ions. These spectra are obtained using the “tagging” approach carried out with photofragmentation tandem mass spectrometry. In the isolated cations, we find that the oxygen atom on the ether chain binds exclusively to the acidic C(2)H position on the Im+ ring. Upon complexation with BF4– to form the ternary (ether-MIm+)2(BF4–) cation, however, the less acidic C(4,5)H groups also participate as contact points for the ionic assembly, in contrast to the behavior of the closely related (EMIm+)2(BF4–) system. These experimental results support the conclusions derived from earlier X-ray scattering and molecular dynamics results on bulk ILs regarding interactions with the ring CH groups and their implications on tuning the viscosities of this class of functionalized ILs.
- Authors:
-
- Yale Univ., New Haven, CT (United States)
- Queensborough Community College of the City University of New York, Bayside, NY (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States); Yale Univ., New Haven, CT (United States)
- Sponsoring Org.:
- US Air Force Office of Scientific Research (AFOSR); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1558252
- Alternate Identifier(s):
- OSTI ID: 1594124
- Report Number(s):
- BNL-212010-2019-JAAM
Journal ID: ISSN 1089-5639
- Grant/Contract Number:
- SC0012704; FG02-06ER15800; FA9550-17-1-0267; FA9550-18-1-0213
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
- Additional Journal Information:
- Journal Volume: 123; Journal Issue: 39; Journal ID: ISSN 1089-5639
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ionic liquids; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ethers; Chemical structure; Anions; Molecular structure; Cations; Mass Spectrometry; Infrared Spectroscopy
Citation Formats
Zeng, Helen J., Johnson, Mark A., Ramdihal, Jasodra D., Sumner, Rawlric A., Rodriguez, Chanele, Lall-Ramnarine, Sharon I., and Wishart, James F. Spectroscopic Assessment of Intra- and Intermolecular Hydrogen Bonding in Ether-Functionalized Imidazolium Ionic Liquids. United States: N. p., 2019.
Web. doi:10.1021/acs.jpca.9b04345.
Zeng, Helen J., Johnson, Mark A., Ramdihal, Jasodra D., Sumner, Rawlric A., Rodriguez, Chanele, Lall-Ramnarine, Sharon I., & Wishart, James F. Spectroscopic Assessment of Intra- and Intermolecular Hydrogen Bonding in Ether-Functionalized Imidazolium Ionic Liquids. United States. https://doi.org/10.1021/acs.jpca.9b04345
Zeng, Helen J., Johnson, Mark A., Ramdihal, Jasodra D., Sumner, Rawlric A., Rodriguez, Chanele, Lall-Ramnarine, Sharon I., and Wishart, James F. Fri .
"Spectroscopic Assessment of Intra- and Intermolecular Hydrogen Bonding in Ether-Functionalized Imidazolium Ionic Liquids". United States. https://doi.org/10.1021/acs.jpca.9b04345. https://www.osti.gov/servlets/purl/1558252.
@article{osti_1558252,
title = {Spectroscopic Assessment of Intra- and Intermolecular Hydrogen Bonding in Ether-Functionalized Imidazolium Ionic Liquids},
author = {Zeng, Helen J. and Johnson, Mark A. and Ramdihal, Jasodra D. and Sumner, Rawlric A. and Rodriguez, Chanele and Lall-Ramnarine, Sharon I. and Wishart, James F.},
abstractNote = {Functionalization of the imidazolium (Im+) cationic component of ionic liquids (ILs) with ether chains affords the possibility of tuning their properties through manipulation of the resulting interion and intramolecular interactions. Herein, we quantify these interactions at the molecular level through analysis of the vibrational spectra displayed by size-selected and cryogenically cooled ions. These spectra are obtained using the “tagging” approach carried out with photofragmentation tandem mass spectrometry. In the isolated cations, we find that the oxygen atom on the ether chain binds exclusively to the acidic C(2)H position on the Im+ ring. Upon complexation with BF4– to form the ternary (ether-MIm+)2(BF4–) cation, however, the less acidic C(4,5)H groups also participate as contact points for the ionic assembly, in contrast to the behavior of the closely related (EMIm+)2(BF4–) system. These experimental results support the conclusions derived from earlier X-ray scattering and molecular dynamics results on bulk ILs regarding interactions with the ring CH groups and their implications on tuning the viscosities of this class of functionalized ILs.},
doi = {10.1021/acs.jpca.9b04345},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 39,
volume = 123,
place = {United States},
year = {Fri Aug 16 00:00:00 EDT 2019},
month = {Fri Aug 16 00:00:00 EDT 2019}
}
Web of Science