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

Niemann, Thomas; Strate, Anne; Ludwig, Ralf; Zeng, Helen J.; Menges, Fabian S.; Johnson, Mark A.

doi:10.1039/C9CP03300A

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

Journal Article · Tue Jul 30 00:00:00 EDT 2019 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/C9CP03300A· OSTI ID:1594141

Niemann, Thomas ^[1]; Strate, Anne ^[1];

^[2];

^[3];

^[3]

Univ. of Rostock (Germany)
Univ. of Rostock (Germany); Leibniz-Inst. für Katalyse, Rostock (Germany)
Yale Univ., New Haven, CT (United States)

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.

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Research Organization:: Yale Univ., New Haven, CT (United States)

Sponsoring Organization:: USDOE Office of Science (SC); US Air Force Office of Scientific Research (AFOSR); German Research Foundation (DFG)

Grant/Contract Number:: FG02-06ER15800; FA9550-17-1-0267; FA9550-18-1-0213; LU 506/14-1

OSTI ID:: 1594141

Alternate ID(s):: OSTI ID: 1547635

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Vol. 21, Issue 33; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 26 works

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Hydrogen Bonding Between Ions of Like Charge in Ionic Liquids Characterized by NMR Deuteron Quadrupole Coupling Constants—Comparison with Salt Bridges and Molecular Systems Khudozhitkov, Alexander E.; Neumann, Jan; Niemann, Thomas Angewandte Chemie, Vol. 131, Issue 49 https://doi.org/10.1002/ange.201912476	journal	October 2019
Hydrogen Bonding Between Ions of Like Charge in Ionic Liquids Characterized by NMR Deuteron Quadrupole Coupling Constants—Comparison with Salt Bridges and Molecular Systems Khudozhitkov, Alexander E.; Neumann, Jan; Niemann, Thomas Angewandte Chemie International Edition, Vol. 58, Issue 49 https://doi.org/10.1002/anie.201912476	journal	December 2019
Controlling “like–likes–like” charge attraction in hydroxy-functionalized ionic liquids by polarizability of the cations, interaction strength of the anions and varying alkyl chain length Niemann, Thomas; Zaitsau, Dzmitry H.; Strate, Anne Physical Chemistry Chemical Physics, Vol. 22, Issue 5 https://doi.org/10.1039/c9cp06481h	journal	January 2020

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
chemical structure
anions
molecular structure
cations
ionic liquids
mass spectrometry
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