Spectroscopic Assessment of Intra- and Intermolecular Hydrogen Bonding in Ether-Functionalized Imidazolium Ionic Liquids

Zeng, Helen J.; Johnson, Mark A.; Ramdihal, Jasodra D.; Sumner, Rawlric A.; Rodriguez, Chanele; Lall-Ramnarine, Sharon I.; Wishart, James F.

doi:10.1021/acs.jpca.9b04345

Title: Spectroscopic Assessment of Intra- and Intermolecular Hydrogen Bonding in Ether-Functionalized Imidazolium Ionic Liquids

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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:

Zeng, Helen J. ^[1];

^[1]; Ramdihal, Jasodra D. ^[2]; Sumner, Rawlric A. ^[2]; Rodriguez, Chanele ^[2]; Lall-Ramnarine, Sharon I. ^[2];

^[3]

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:: Fri Aug 16 00:00:00 EDT 2019

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.

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                    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

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                    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.

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@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}

}

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