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Title: Ionic Liquid–Solute Interactions Studied by 2D NOE NMR Spectroscopy

Abstract

Intermolecular interactions between a Ru²⁺(bpy)₃ solute and the anions and cations of four different ionic liquids (ILs) are investigated by 2D NMR nuclear Overhauser effect (NOE) techniques, including {¹H-¹⁹F} HOESY and {¹H-¹H} ROESY. Four ILs are studied, each having the same bis(trifluoromethylsulfonyl)amide anion in common. Two of the ILs have aliphatic 1-alkyl-1-methylpyrrolidinium cations, while the other two ILs have aromatic 1-alkyl-3-methylimidazolium cations. ILs with both shorter (butyl) and longer (octyl or decyl) cationic alkyl substituents are studied. NOE NMR results suggest that the local environment of IL anions and cations near the Ru²⁺(bpy)₃ solute is rather different from the bulk IL structure. The solute-anion and solute-cation interactions are significantly different both for ILs with short vs long alkyl tails and for ILs with aliphatic vs aromatic cation polar head groups. In particular, the solute-anion interactions are observed to be about 3 times stronger for the cations with shorter alkyl tails relative to the ILs with longer alkyl tails. The Ru²⁺(bpy)₃ solute interacts with both the polar head and the nonpolar tail groups of the 1- butyl-1-methylpyrrolidinium cation but only with the nonpolar tail groups of the 1-decyl-1-methylpyrrolidinium cation.

Authors:
 [1];  [1]
+ Show Author Affiliations
  1. Rutgers Univ., Piscataway, NJ (United States). Depts. of Chemistry and Chemical Biology
Publication Date:
Research Org.:
Rutgers Univ., Piscataway, NJ (United States)
Sponsoring Org.:
USDOE Advanced Research Projects Agency - Energy (ARPA-E)
OSTI Identifier:
1173218
Grant/Contract Number:  
SC0001780
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 119; Journal Issue: 29; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ionic liquid; ion-solute interactions; NOE, HOESY, ROESY, 2D-NMR

Citation Formats

Khatun, Sufia, and Castner, Edward W. Ionic Liquid–Solute Interactions Studied by 2D NOE NMR Spectroscopy. United States: N. p., 2014. Web. doi:10.1021/jp509861g.
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Khatun, Sufia, & Castner, Edward W. Ionic Liquid–Solute Interactions Studied by 2D NOE NMR Spectroscopy. United States. https://doi.org/10.1021/jp509861g
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Khatun, Sufia, and Castner, Edward W. Wed . "Ionic Liquid–Solute Interactions Studied by 2D NOE NMR Spectroscopy". United States. https://doi.org/10.1021/jp509861g. https://www.osti.gov/servlets/purl/1173218.
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@article{osti_1173218,
title = {Ionic Liquid–Solute Interactions Studied by 2D NOE NMR Spectroscopy},
author = {Khatun, Sufia and Castner, Edward W.},
abstractNote = {Intermolecular interactions between a Ru²⁺(bpy)₃ solute and the anions and cations of four different ionic liquids (ILs) are investigated by 2D NMR nuclear Overhauser effect (NOE) techniques, including {¹H-¹⁹F} HOESY and {¹H-¹H} ROESY. Four ILs are studied, each having the same bis(trifluoromethylsulfonyl)amide anion in common. Two of the ILs have aliphatic 1-alkyl-1-methylpyrrolidinium cations, while the other two ILs have aromatic 1-alkyl-3-methylimidazolium cations. ILs with both shorter (butyl) and longer (octyl or decyl) cationic alkyl substituents are studied. NOE NMR results suggest that the local environment of IL anions and cations near the Ru²⁺(bpy)₃ solute is rather different from the bulk IL structure. The solute-anion and solute-cation interactions are significantly different both for ILs with short vs long alkyl tails and for ILs with aliphatic vs aromatic cation polar head groups. In particular, the solute-anion interactions are observed to be about 3 times stronger for the cations with shorter alkyl tails relative to the ILs with longer alkyl tails. The Ru²⁺(bpy)₃ solute interacts with both the polar head and the nonpolar tail groups of the 1- butyl-1-methylpyrrolidinium cation but only with the nonpolar tail groups of the 1-decyl-1-methylpyrrolidinium cation.},
doi = {10.1021/jp509861g},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 29,
volume = 119,
place = {United States},
year = {2014},
month = {11}
}
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Pair dynamics and the intermolecular nuclear Overhauser effect (NOE) in liquids analysed by simulation and model theories: Application to an ionic liquid
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  • The Journal of Chemical Physics, Vol. 140, Issue 18
  • DOI: 10.1063/1.4874155
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    Design Principles of Ionic Liquids for Transdermal Drug Delivery
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    • Tanner, Eden E. L.; Curreri, Alexander M.; Balkaran, Joel P. R.
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    • Physical Chemistry Chemical Physics, Vol. 20, Issue 19
    • DOI: 10.1039/c8cp00911b
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