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Title: Chain Length Dependence of Hydrogen Bond Linkages between Cationic Constituents in Hydroxy-Functionalized Ionic Liquids: Tracking Bulk Behavior to the Molecular Level with Cold Cluster Ion Spectroscopy

Abstract

Hydroxy functionalization of cations in ionic liquids (ILs) can lead to formation of contacts between their OH groups [so-called (c–c) interactions]. One class of these linkages involves cooperatively enhanced hydrogen bonds to anionic partners that are sufficiently strong to overcome the repulsion between two positively charged centers. Herein, we clarify how the propensity for the formation of (c–c) contacts depends on the alkyl chain length between two cationic rings and their OH groups by analyzing the temperature-dependent IR spectra of bulk ILs as well as the vibrational predissociation spectra of ~35 K complexes comprised of two cations and one anion. This study compares the behavior of two cationic derivatives with ethyl and propyl chains complexed with two different anions: bis(trifluoromethylsulfonyl)imide and tetrafluoroborate. Only the bulk ILs with the longer chain propyl derivative [HPMPip+ = 1-(3-hydroxypropyl)-1-methylpiperidinium] display (c–c) interactions. Finally, molecular-level aspects of this docking arrangement are revealed by analyzing the OH stretching fundamentals displayed by the ternary complexes.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2];  [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Yale Univ., New Haven, CT (United States). Sterling Chemistry Lab.
  2. Univ. of Rostock (Germany). Dept. of Chemistry and Dept. Life, Light & Matter
  3. Univ. of Rostock (Germany). Dept. of Chemistry and Dept. Life, Light & Matter; Leibniz-Inst. für Katalyse, Rostock (Germany)
Publication Date:
Research Org.:
Yale Univ., New Haven, CT (United States)
Sponsoring Org.:
USDOE Office of Science (SC); US Air Force Office of Scientific Research (AFOSR); German Research Foundation (DFG)
OSTI Identifier:
1594083
Grant/Contract Number:  
FG02-06ER15800; FA9550-17-1-0267; LU-506/14-1; LU-506/14-2
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 11; Journal Issue: 3; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ionic Liquids; Mass Spectrometry; Infrared Spectroscopy

Citation Formats

Zeng, Helen J., Menges, Fabian S., Niemann, Thomas, Strate, Anne, Ludwig, Ralf, and Johnson, Mark A. Chain Length Dependence of Hydrogen Bond Linkages between Cationic Constituents in Hydroxy-Functionalized Ionic Liquids: Tracking Bulk Behavior to the Molecular Level with Cold Cluster Ion Spectroscopy. United States: N. p., 2020. Web. https://doi.org/10.1021/acs.jpclett.9b03359.
Zeng, Helen J., Menges, Fabian S., Niemann, Thomas, Strate, Anne, Ludwig, Ralf, & Johnson, Mark A. Chain Length Dependence of Hydrogen Bond Linkages between Cationic Constituents in Hydroxy-Functionalized Ionic Liquids: Tracking Bulk Behavior to the Molecular Level with Cold Cluster Ion Spectroscopy. United States. https://doi.org/10.1021/acs.jpclett.9b03359
Zeng, Helen J., Menges, Fabian S., Niemann, Thomas, Strate, Anne, Ludwig, Ralf, and Johnson, Mark A. Fri . "Chain Length Dependence of Hydrogen Bond Linkages between Cationic Constituents in Hydroxy-Functionalized Ionic Liquids: Tracking Bulk Behavior to the Molecular Level with Cold Cluster Ion Spectroscopy". United States. https://doi.org/10.1021/acs.jpclett.9b03359. https://www.osti.gov/servlets/purl/1594083.
@article{osti_1594083,
title = {Chain Length Dependence of Hydrogen Bond Linkages between Cationic Constituents in Hydroxy-Functionalized Ionic Liquids: Tracking Bulk Behavior to the Molecular Level with Cold Cluster Ion Spectroscopy},
author = {Zeng, Helen J. and Menges, Fabian S. and Niemann, Thomas and Strate, Anne and Ludwig, Ralf and Johnson, Mark A.},
abstractNote = {Hydroxy functionalization of cations in ionic liquids (ILs) can lead to formation of contacts between their OH groups [so-called (c–c) interactions]. One class of these linkages involves cooperatively enhanced hydrogen bonds to anionic partners that are sufficiently strong to overcome the repulsion between two positively charged centers. Herein, we clarify how the propensity for the formation of (c–c) contacts depends on the alkyl chain length between two cationic rings and their OH groups by analyzing the temperature-dependent IR spectra of bulk ILs as well as the vibrational predissociation spectra of ~35 K complexes comprised of two cations and one anion. This study compares the behavior of two cationic derivatives with ethyl and propyl chains complexed with two different anions: bis(trifluoromethylsulfonyl)imide and tetrafluoroborate. Only the bulk ILs with the longer chain propyl derivative [HPMPip+ = 1-(3-hydroxypropyl)-1-methylpiperidinium] display (c–c) interactions. Finally, molecular-level aspects of this docking arrangement are revealed by analyzing the OH stretching fundamentals displayed by the ternary complexes.},
doi = {10.1021/acs.jpclett.9b03359},
journal = {Journal of Physical Chemistry Letters},
number = 3,
volume = 11,
place = {United States},
year = {2020},
month = {1}
}

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