Communication: Spectroscopic characterization of a strongly interacting C(2)H group on the EMIM + cation in the (EMIM+ )2X- (X = BF4, Cl, Br, and I) ternary building blocks of ionic liquids

Gorlova, Olga; Craig, Stephanie M.; Johnson, Mark A.

doi:10.1063/1.5009009

Title: Communication: Spectroscopic characterization of a strongly interacting C₍₂₎H group on the EMIM ⁺ cation in the (EMIM⁺ )₂X^- (X = BF₄, Cl, Br, and I) ternary building blocks of ionic liquids

Journal Article · Fri Dec 15 00:00:00 EST 2017 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5009009· OSTI ID:1512953

Gorlova, Olga ^[1]; Craig, Stephanie M. ^[1];

^[1]

Yale Univ., New Haven, CT (United States)

Here, to unravel the intermolecular interactions at play in the assemblies of EMIM-based ionic liquids, we report the vibrational spectra of the cryogenically cooled, cationic ternary complexes with halide ions, (EMIM⁺)₂X^-, X = Cl, Br, and I. This series specifically addresses the spectral response of the acidic C₍₂₎H group upon complexation with an atomic anion, which is isolated by selective deuteration at this position. Unlike the behavior of the related BF4- complex, the halide systems display large (~175 cm^-1) red-shifts and dramatic (~30X) intensity enhancements in the C₍₂₎D stretch (relative to that of the bare d₍₂₎-EMIM⁺ cation), which are largest for the chloride anion. Lastly, electronic structure calculations indicate that, while the spectroscopic signatures of the interaction follow those expected for a traditional hydrogen bond to the C₍₂₎H group, the C–H–X docking arrangement deviates substantially from linearity due to a “double contact” motif involving a weaker interaction to the nearby methyl group [Hunt et al., Chem. Soc. Rev. 44(5), 1257–1288 (2015)].

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

Sponsoring Organization:: USDOE

Grant/Contract Number:: FG02-06ER15800; FG02-00ER15800

OSTI ID:: 1512953

Alternate ID(s):: OSTI ID: 1413549

Journal Information:: Journal of Chemical Physics, Vol. 147, Issue 23; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 6 works

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References (37)

Room-Temperature Ionic Liquids: Solvents for Synthesis and Catalysis. 2 Hallett, Jason P.; Welton, Tom Chemical Reviews, Vol. 111, Issue 5 https://doi.org/10.1021/cr1003248	journal	May 2011
Ionic-liquid materials for the electrochemical challenges of the future Armand, Michel; Endres, Frank; MacFarlane, Douglas R. Nature Materials, Vol. 8, Issue 8, p. 621-629 https://doi.org/10.1038/nmat2448	journal	July 2009
Ionic Liquids: New Perspectives for Inorganic Synthesis? Freudenmann, Dominic; Wolf, Silke; Wolff, Michael Angewandte Chemie International Edition, Vol. 50, Issue 47 https://doi.org/10.1002/anie.201100904	journal	October 2011
Ultrafast transient absorption spectrum of the room temperature Ionic liquid 1-hexyl-3-methylimidazolium bromide: Confounding effects of photo-degradation Musat, Raluca M.; Crowell, Robert A.; Polyanskiy, Dmitriy E. Radiation Physics and Chemistry, Vol. 117 https://doi.org/10.1016/j.radphyschem.2015.07.015	journal	December 2015
The Structure of Imidazolium-Based Ionic Liquids: Insights From Ion-Pair Interactions Hunt, Patricia A.; Gould, Ian R.; Kirchner, Barbara Australian Journal of Chemistry, Vol. 60, Issue 1 https://doi.org/10.1071/ch06301	journal	January 2007
Physical Properties and Intermolecular Dynamics of an Ionic Liquid Compared with Its Isoelectronic Neutral Binary Solution Shirota, Hideaki; Castner, Edward W. The Journal of Physical Chemistry A, Vol. 109, Issue 42 https://doi.org/10.1021/jp054664c	journal	October 2005
Identification of multiple conformers of the ionic liquid [emim][tf2n] in the gas phase using IR/UV action spectroscopy Booth, Ryan S.; Annesley, Christopher J.; Young, Justin W. Physical Chemistry Chemical Physics, Vol. 18, Issue 25 https://doi.org/10.1039/c6cp02657e	journal	January 2016
Vibrational predissociation spectroscopy of the H2-tagged mono- and dicarboxylate anions of dodecanedioic acid Kamrath, Michael Z.; Relph, Rachael A.; Guasco, Timothy L. International Journal of Mass Spectrometry, Vol. 300, Issue 2-3 https://doi.org/10.1016/j.ijms.2010.10.021	journal	March 2011
Ionic Liquids as Hypergolic Fuels Zhang, Yanqiang; Gao, Haixiang; Joo, Young-Hyuk Angewandte Chemie International Edition, Vol. 50, Issue 41 https://doi.org/10.1002/anie.201101954	journal	September 2011
Helium Nanodroplet Isolation and Infrared Spectroscopy of the Isolated Ion-Pair 1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide Obi, Emmanuel I.; Leavitt, Christopher M.; Raston, Paul L. The Journal of Physical Chemistry A, Vol. 117, Issue 37 https://doi.org/10.1021/jp4078322	journal	September 2013
How ionic liquids can help to stabilize native proteins Weingärtner, Hermann; Cabrele, Chiara; Herrmann, Christian Phys. Chem. Chem. Phys., Vol. 14, Issue 2 https://doi.org/10.1039/c1cp21947b	journal	January 2012
Comparison of the local binding motifs in the imidazolium-based ionic liquids [EMIM][BF ₄ ] and [EMMIM][BF ₄ ] through cryogenic ion vibrational predissociation spectroscopy: Unraveling the roles of anharmonicity and intermolecular interactions Fournier, Joseph A.; Wolke, Conrad T.; Johnson, Christopher J. The Journal of Chemical Physics, Vol. 142, Issue 6 https://doi.org/10.1063/1.4907199	journal	February 2015
Ionic Liquid-Mediated Selective Conversion of CO₂ to CO at Low Overpotentials Rosen, B. A.; Salehi-Khojin, A.; Thorson, M. R. Science, Vol. 334, Issue 6056, p. 643-644 https://doi.org/10.1126/science.1209786	journal	September 2011
Energy applications of ionic liquids Wishart, James F. Energy & Environmental Science, Vol. 2, Issue 9 https://doi.org/10.1039/b906273d	journal	January 2009
Unique Spatial Heterogeneity in Ionic Liquids Wang, Yanting; Voth, Gregory A. Journal of the American Chemical Society, Vol. 127, Issue 35 https://doi.org/10.1021/ja053796g	journal	September 2005
Nanoscale Segregation in Room Temperature Ionic Liquids ^† Triolo, Alessandro; Russina, Olga; Bleif, Hans-Jurgen The Journal of Physical Chemistry B, Vol. 111, Issue 18 https://doi.org/10.1021/jp067705t	journal	May 2007
Characterising the Electronic Structure of Ionic Liquids: An Examination of the 1-Butyl-3-Methylimidazolium Chloride Ion Pair Hunt, Patricia A.; Kirchner, Barbara; Welton, Tom Chemistry - A European Journal, Vol. 12, Issue 26 https://doi.org/10.1002/chem.200600103	journal	September 2006
NMR studies of ionic liquids: Structure and dynamics Weingärtner, Hermann Current Opinion in Colloid & Interface Science, Vol. 18, Issue 3 https://doi.org/10.1016/j.cocis.2013.04.001	journal	June 2013
Nature of Hydrogen Bonding in Charged Hydrogen-Bonded Complexes and Imidazolium-Based Ionic Liquids Izgorodina, Ekaterina I.; MacFarlane, Douglas R. The Journal of Physical Chemistry B, Vol. 115, Issue 49 https://doi.org/10.1021/jp208150b	journal	December 2011
Hypergolic Ionic Liquids with the 2,2-Dialkyltriazanium Cation Gao, Haixiang; Joo, Young-Hyuk; Twamley, Brendan Angewandte Chemie International Edition, Vol. 48, Issue 15 https://doi.org/10.1002/anie.200900094	journal	March 2009
Electrochemical Reactivity in Room-Temperature Ionic Liquids Hapiot, Philippe; Lagrost, Corinne Chemical Reviews, Vol. 108, Issue 7 https://doi.org/10.1021/cr0680686	journal	July 2008
Proton sharing in hydronium–nitrogen clusters probed with infrared spectroscopy Bandyopadhyay, B.; Cheng, T. C.; Duncan, M. A. International Journal of Mass Spectrometry, Vol. 297, Issue 1-3 https://doi.org/10.1016/j.ijms.2010.07.010	journal	November 2010
IR and UV Spectroscopy of Vapor-Phase Jet-Cooled Ionic Liquid [emim] ⁺ [Tf ₂ N] ⁻ : Ion Pair Structure and Photodissociation Dynamics Cooper, Russell; Zolot, Alexander M.; Boatz, Jerry A. The Journal of Physical Chemistry A, Vol. 117, Issue 47 https://doi.org/10.1021/jp409670n	journal	November 2013
Gas Solubility in Ionic Liquids Lei, Zhigang; Dai, Chengna; Chen, Biaohua Chemical Reviews, Vol. 114, Issue 2 https://doi.org/10.1021/cr300497a	journal	November 2013
Hydrogen bonding in ionic liquids Hunt, Patricia A.; Ashworth, Claire R.; Matthews, Richard P. Chemical Society Reviews, Vol. 44, Issue 5 https://doi.org/10.1039/c4cs00278d	journal	January 2015
On the physical origin of the cation–anion intermediate bond in ionic liquids Part I. Placing a (weak) hydrogen bond between two charges Lehmann, Sebastian B. C.; Roatsch, Martin; Schöppke, Matthias Physical Chemistry Chemical Physics, Vol. 12, Issue 27 https://doi.org/10.1039/b921246a	journal	January 2010
Ionic liquids from the bottom up: Local assembly motifs in [EMIM][BF ₄ ] through cryogenic ion spectroscopy Johnson, Christopher J.; Fournier, Joseph A.; Wolke, Conrad T. The Journal of Chemical Physics, Vol. 139, Issue 22 https://doi.org/10.1063/1.4838475	journal	December 2013
Ionic liquids as electrolytes Galiński, Maciej; Lewandowski, Andrzej; Stępniak, Izabela Electrochimica Acta, Vol. 51, Issue 26 https://doi.org/10.1016/j.electacta.2006.03.016	journal	August 2006
Understanding the ionic liquid [NC ₄₁₁₁ ][NTf ₂ ] from individual building blocks: an IR-spectroscopic study Hanke, Kenny; Kaufmann, Matin; Schwaab, Gerhard Physical Chemistry Chemical Physics, Vol. 17, Issue 13 https://doi.org/10.1039/c5cp00116a	journal	January 2015
Theoretical analysis of the hydrogen bond of imidazolium C2–H with anions Tsuzuki, Seiji; Tokuda, Hiroyuki; Mikami, Masuhiro Physical Chemistry Chemical Physics, Vol. 9, Issue 34 https://doi.org/10.1039/b707419k	journal	January 2007
Quantum Chemical Modeling of Hydrogen Bonding in Ionic Liquids Hunt, Patricia A. Topics in Current Chemistry, Vol. 375, Issue 3 https://doi.org/10.1007/s41061-017-0142-7	journal	May 2017
Anharmonic modeling of the conformation-specific IR spectra of ethyl, n -propyl, and n -butylbenzene Tabor, Daniel P.; Hewett, Daniel M.; Bocklitz, Sebastian The Journal of Chemical Physics, Vol. 144, Issue 22 https://doi.org/10.1063/1.4953181	journal	June 2016
Tuning the intermolecular proton bond in the H5<mml:math altimg="si1.gif" overflow="scroll" xmlns:xocs="http://www.elsevier.com/xml/xocs/dtd" xmlns:xs="http://www.w3.org/2001/XMLSchema" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xmlns="http://www.elsevier.com/xml/ja/dtd" xmlns:ja="http://www.elsevier.com/xml/ja/dtd" xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:tb="http://www.elsevier.com/xml/common/table/dtd" xmlns:sb="http://www.elsevier.com/xml/common/struct-bib/dtd" xmlns:ce="http://www.elsevier.com/xml/common/dtd" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:cals="http://www.elsevier.com/xml/common/cals/dtd"><mml:mrow><mml:msubsup><mml:mrow><mml:mtext>O</mml:mtext></mml:mrow><mml:mrow><mml:mn>2</mml:mn></mml:mrow><mml:mrow><mml:mo>+</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math> ‘Zundel ion’ scaffold Olesen, S. G.; Guasco, T. L.; Roscioli, J. R. Chemical Physics Letters, Vol. 509, Issue 4-6 https://doi.org/10.1016/j.cplett.2011.04.060	journal	June 2011
CHEMISTRY: Ionic Liquids--Solvents of the Future? Rogers, R. D.; Seddon, Kenneth R. Science, Vol. 302, Issue 5646, p. 792-793 https://doi.org/10.1126/science.1090313	journal	October 2003
Structure and Nanostructure in Ionic Liquids Hayes, Robert; Warr, Gregory G.; Atkin, Rob Chemical Reviews, Vol. 115, Issue 13 https://doi.org/10.1021/cr500411q	journal	June 2015
Hidden role of intermolecular proton transfer in the anomalously diffuse vibrational spectrum of a trapped hydronium ion Craig, Stephanie M.; Menges, Fabian S.; Duong, Chinh H. Proceedings of the National Academy of Sciences, Vol. 114, Issue 24 https://doi.org/10.1073/pnas.1705089114	journal	May 2017
Features in Vibrational Spectra Induced by Ar-Tagging for H ₃ O ⁺ Ar _m , m = 0–3 Li, Jheng-Wei; Morita, Masato; Takahashi, Kaito The Journal of Physical Chemistry A, Vol. 119, Issue 44 https://doi.org/10.1021/acs.jpca.5b08898	journal	October 2015

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Title: Communication: Spectroscopic characterization of a strongly interacting C(2)H group on the EMIM + cation in the (EMIM+ )2X- (X = BF4, Cl, Br, and I) ternary building blocks of ionic liquids

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Title: Communication: Spectroscopic characterization of a strongly interacting C₍₂₎H group on the EMIM ⁺ cation in the (EMIM⁺ )₂X^- (X = BF₄, Cl, Br, and I) ternary building blocks of ionic liquids