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Title: Cooperatively enhanced hydrogen bonds in ionic liquids: closing the loop with molecular mimics of hydroxy-functionalized cations

Abstract

Here, we address the cooperative hydrogen bonding interactions in play between the ionic constituents of ionic liquids (ILs) with particular attention to those involving the attractive interactions between two cations in the system 1-(2-hydroxyethyl)pyridinium tetrafluoroborate [HEPy][BF4]. This is accomplished by comparing the temperature-dependent linear infrared spectra of [HEPy][BF4] with that of the molecular mimic of its cation, 2-phenylethanol (PhenEthOH). We then explored the structural motifs of these H-bonded configurations at the molecular level by analyzing the cryogenic ion vibrational predissociation spectroscopy of cold (~35 K) gas phase cluster ions with quantum chemical methods. The analysis of the OH stretching bands reveals the formation of the various binding motifs ranging from the common +OH∙∙∙BF4- interaction in ion-pairs (c–a) to the unusual +OH∙∙∙+OH interaction (c–c) in linear and cyclic, homodromic H-bonding domains. Replacing ion-pairs by the molecular (neutral) analogue of the IL cation also results in the formation of positively charged cyclic motifs, with the bands of the gas phase cationic cyclic tetramer (HEPy+)(PhenEthOH)3 appearing quite close to those assigned previously to cyclic tetramers in the liquid. These conclusions are supported by density functional theory (DFT) calculations of the cationic and neutral clusters as well as the local structures in the liquid.more » Our combined experimental and theoretical approach for the gas and the liquid phases provides important insight into the competition between differently H-bonded and charged constituents in liquids.« less

Authors:
 [1];  [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [3]
+ Show Author Affiliations
  1. Univ. of Rostock (Germany)
  2. Univ. of Rostock (Germany); Leibniz-Inst. für Katalyse, Rostock (Germany)
  3. Yale Univ., New Haven, CT (United States)
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:
1594141
Alternate Identifier(s):
OSTI ID: 1547635
Grant/Contract Number:  
FG02-06ER15800; FA9550-17-1-0267; FA9550-18-1-0213; LU 506/14-1
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 21; Journal Issue: 33; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemical structure; anions; molecular structure; cations; ionic liquids; mass spectrometry; infrared spectroscopy

Citation Formats

Niemann, Thomas, Strate, Anne, Ludwig, Ralf, Zeng, Helen J., Menges, Fabian S., and Johnson, Mark A. Cooperatively enhanced hydrogen bonds in ionic liquids: closing the loop with molecular mimics of hydroxy-functionalized cations. United States: N. p., 2019. Web. doi:10.1039/C9CP03300A.
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Niemann, Thomas, Strate, Anne, Ludwig, Ralf, Zeng, Helen J., Menges, Fabian S., & Johnson, Mark A. Cooperatively enhanced hydrogen bonds in ionic liquids: closing the loop with molecular mimics of hydroxy-functionalized cations. United States. https://doi.org/10.1039/C9CP03300A
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Niemann, Thomas, Strate, Anne, Ludwig, Ralf, Zeng, Helen J., Menges, Fabian S., and Johnson, Mark A. Tue . "Cooperatively enhanced hydrogen bonds in ionic liquids: closing the loop with molecular mimics of hydroxy-functionalized cations". United States. https://doi.org/10.1039/C9CP03300A. https://www.osti.gov/servlets/purl/1594141.
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@article{osti_1594141,
title = {Cooperatively enhanced hydrogen bonds in ionic liquids: closing the loop with molecular mimics of hydroxy-functionalized cations},
author = {Niemann, Thomas and Strate, Anne and Ludwig, Ralf and Zeng, Helen J. and Menges, Fabian S. and Johnson, Mark A.},
abstractNote = {Here, we address the cooperative hydrogen bonding interactions in play between the ionic constituents of ionic liquids (ILs) with particular attention to those involving the attractive interactions between two cations in the system 1-(2-hydroxyethyl)pyridinium tetrafluoroborate [HEPy][BF4]. This is accomplished by comparing the temperature-dependent linear infrared spectra of [HEPy][BF4] with that of the molecular mimic of its cation, 2-phenylethanol (PhenEthOH). We then explored the structural motifs of these H-bonded configurations at the molecular level by analyzing the cryogenic ion vibrational predissociation spectroscopy of cold (~35 K) gas phase cluster ions with quantum chemical methods. The analysis of the OH stretching bands reveals the formation of the various binding motifs ranging from the common +OH∙∙∙BF4- interaction in ion-pairs (c–a) to the unusual +OH∙∙∙+OH interaction (c–c) in linear and cyclic, homodromic H-bonding domains. Replacing ion-pairs by the molecular (neutral) analogue of the IL cation also results in the formation of positively charged cyclic motifs, with the bands of the gas phase cationic cyclic tetramer (HEPy+)(PhenEthOH)3 appearing quite close to those assigned previously to cyclic tetramers in the liquid. These conclusions are supported by density functional theory (DFT) calculations of the cationic and neutral clusters as well as the local structures in the liquid. Our combined experimental and theoretical approach for the gas and the liquid phases provides important insight into the competition between differently H-bonded and charged constituents in liquids.},
doi = {10.1039/C9CP03300A},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 33,
volume = 21,
place = {United States},
year = {Tue Jul 30 00:00:00 EDT 2019},
month = {Tue Jul 30 00:00:00 EDT 2019}
}
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Journal Article:
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https://doi.org/10.1039/C9CP03300A
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Cited by: 26 works
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Figures / Tables:

Scheme 1 Scheme 1: Illustrations explaining the concept of this study. The identification of the structural motifs can be achieved by liquid and gas phase IR spectroscopies. (a) Cyclic tetramers (c+)4(a‾)4, fully compensated by counter anions in the neutral bulk system. (b) Neutral cyclic tetramers (c+)2(a‾)2(m)2 in the bulk phase, wherein ion-pairsmore » (c+)(a‾) (circled in (b)) are replaced by molecules (m). (c) Positively charged cyclic tetramers (c+)(m)3 in the gas phase. (d) Positively charged cyclic tetramers (c+)4(a‾)3 in the gas phase, with stronger Coulomb repulsion by removing one counter anion.« less
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    Works referencing / citing this record:

    Hydrogen Bonding Between Ions of Like Charge in Ionic Liquids Characterized by NMR Deuteron Quadrupole Coupling Constants—Comparison with Salt Bridges and Molecular Systems
    journal, December 2019

    • Khudozhitkov, Alexander E.; Neumann, Jan; Niemann, Thomas
    • Angewandte Chemie International Edition, Vol. 58, Issue 49
    • DOI: 10.1002/anie.201912476
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      Figures / Tables found in this record:

      Scheme 1 (p. 14)figure
      Scheme 2 (p. 15)figure
      Figure 1 (p. 16)figure
      Figure 2 (p. 17)figure
      Figure 3 (p. 18)figure
      Figure 4 (p. 19)figure
      Figure. 5 (p. 20)figure
      Figure 6 (p. 21)figure
      Fig. S1 (p. 37)figure
      Fig. S2 (p. 37)figure
      Fig. S3 (p. 38)figure
      Fig. S4 (p. 38)figure
      Table S1 (p. 39)table
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