skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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]
  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:
Journal Article: 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.
Khatun, Sufia, & Castner, Edward W. Ionic Liquid–Solute Interactions Studied by 2D NOE NMR Spectroscopy. United States. https://doi.org/10.1021/jp509861g
Khatun, Sufia, and Castner, Edward W. 2014. "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.
@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},
url = {https://www.osti.gov/biblio/1173218}, journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
issn = {1520-6106},
number = 29,
volume = 119,
place = {United States},
year = {Wed Nov 26 00:00:00 EST 2014},
month = {Wed Nov 26 00:00:00 EST 2014}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 26 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Ionic Liquids—New “Solutions” for Transition Metal Catalysis
journal, November 2000


Supported Ionic Liquid Phase (SILP) Catalysis: An Innovative Concept for Homogeneous Catalysis in Continuous Fixed-Bed Reactors
journal, February 2006


From Molten Salts to Ionic Liquids: A “Nano” Journey
journal, November 2011


Ionic Liquids in Electrochemical Devices and Processes: Managing Interfacial Electrochemistry
journal, November 2007


Ionic-liquid materials for the electrochemical challenges of the future
journal, July 2009


Dissolution of Cellose with Ionic Liquids
journal, May 2002

  • Swatloski, Richard P.; Spear, Scott K.; Holbrey, John D.
  • Journal of the American Chemical Society, Vol. 124, Issue 18, p. 4974-4975
  • https://doi.org/10.1021/ja025790m

Extraction of lignin from lignocellulose at atmospheric pressure using alkylbenzenesulfonate ionic liquid
journal, January 2009


Solubility of CO 2 , CH 4 , C 2 H 6 , C 2 H 4 , O 2 , and N 2 in 1-Hexyl-3-methylpyridinium Bis(trifluoromethylsulfonyl)imide: Comparison to Other Ionic Liquids
journal, November 2007


Ionic Liquids in Separations
journal, November 2007


Molecular Design of High Capacity, Low Viscosity, Chemically Tunable Ionic Liquids for CO2 Capture
journal, December 2010


Applications of ionic liquids in the chemical industry
journal, January 2008


Room-Temperature Ionic Liquids: Solvents for Synthesis and Catalysis. 2
journal, May 2011


Ionic liquids for energy, materials, and medicine
journal, January 2014


Energy applications of ionic liquids
journal, January 2009


Liquid and Solid-State Structures of 1,3-Dimethylimidazolium Salts
book, August 2003


Nanoscale Segregation in Room Temperature Ionic Liquids
journal, May 2007


Communication: X-ray scattering from ionic liquids with pyrrolidinium cations
journal, March 2011


Structure of ionic liquids of 1-alkyl-3-methylimidazolium cations: A systematic computer simulation study
journal, January 2004


On the Structure and Dynamics of Ionic Liquids
journal, February 2004


Nanostructural Organization in Ionic Liquids
journal, February 2006


Morphology of 1-alkyl-3-methylimidazolium hexafluorophosphate room temperature ionic liquids
journal, May 2008


A Tale of Two Ions:  The Conformational Landscapes of Bis(trifluoromethanesulfonyl)amide and N , N -Dialkylpyrrolidinium
journal, February 2008


Liquid Structure of Room-Temperature Ionic Liquid, 1-Ethyl-3-methylimidazolium Bis-(trifluoromethanesulfonyl) Imide
journal, April 2008


Comparing intermediate range order for alkyl- vs. ether-substituted cations in ionic liquids
journal, January 2012


Temperature-dependent structure of ionic liquids: X-ray scattering and simulations
journal, January 2012


SAXS anti-peaks reveal the length-scales of dual positive–negative and polar–apolar ordering in room-temperature ionic liquids
journal, January 2012


How Does the Ionic Liquid Organizational Landscape Change when Nonpolar Cationic Alkyl Groups Are Replaced by Polar Isoelectronic Diethers?
journal, January 2013


Structure of 1-Alkyl-1-methylpyrrolidinium Bis(trifluoromethylsulfonyl)amide Ionic Liquids with Linear, Branched, and Cyclic Alkyl Groups
journal, July 2013


Neutron diffraction data and molecular dynamics simulations of the molten mixture Ag(Br0.7I0.3)
journal, November 2006


A comparative study of two classical force fields on statics and dynamics of [EMIM][BF4] investigated via molecular dynamics simulations
journal, December 2008


Nuclear Magnetic Resonance Study of the Dynamics of Imidazolium Ionic Liquids with −CH 2 Si(CH 3 ) 3 vs −CH 2 C(CH 3 ) 3 Substituents
journal, May 2007


Collective rotational dynamics in ionic liquids: A computational and experimental study of 1-butyl-3-methyl-imidazolium tetrafluoroborate
journal, February 2007


The surface structure of ionic liquids: Comparing simulations with x-ray measurements
journal, November 2006


Relaxation Processes in Room Temperature Ionic Liquids:  The Case of 1-Butyl-3-Methyl Imidazolium Hexafluorophosphate
journal, November 2005


Small angle neutron scattering from 1-alkyl-3-methylimidazolium hexafluorophosphate ionic liquids ([Cnmim][PF6], n=4, 6, and 8)
journal, August 2010


Interaction between the π-System of Toluene and the Imidazolium Ring of Ionic Liquids: A Combined NMR and Molecular Simulation Study
journal, January 2009


Unique role of hydrophilic ionic liquid in modifying properties of aqueous Triton X-100
journal, November 2007


Surface tension of binary mixtures of imidazolium and ammonium based ionic liquids with alcohols, or water: Cation, anion effect
journal, June 2008


Room temperature ionic liquids as novel media for ‘clean’ liquid–liquid extraction
journal, January 1998


Cooperativity in ionic liquids
journal, May 2006


Structural change of ionic association in ionic liquid/water mixtures: A high-pressure infrared spectroscopic study
journal, March 2009


Raman Investigation of the Ionic Liquid N -Methyl- N -propylpyrrolidinium Bis(trifluoromethanesulfonyl)imide and Its Mixture with LiN(SO 2 CF 3 ) 2
journal, January 2005


Ionic Liquids: Structure and Photochemical Reactions
journal, May 2011


Intermolecular Dynamics, Interactions, and Solvation in Ionic Liquids
journal, November 2007


The phase behaviour of 1-alkyl-3-methylimidazolium tetrafluoroborates; ionic liquids and ionic liquid crystals
journal, January 1999


Do organic solutes experience specific interactions with ionic liquids?
journal, November 2005


Acids and Bases in Ionic Liquids
book, August 2003


Use of ionic liquids in the study of fruit ripening by high-resolution 13C NMR spectroscopy: ‘green’ solvents meet green bananas
journal, January 2006


Solvent–solute interactions in ionic liquids
journal, January 2003


Molecular Solutes in Ionic Liquids: A Structural Perspective
journal, November 2007


Understanding Reactions in Ionic Liquids
book, March 2005


Room-Temperature Ionic Liquids. Solvents for Synthesis and Catalysis
journal, August 1999


Structure and Solvation in Ionic Liquids
journal, November 2007


On the Mechanism of Solvation Dynamics in Imidazolium-Based Ionic Liquids
journal, July 2013


Molecular Dynamics Study of Polarity in Room-Temperature Ionic Liquids
journal, December 2003


Modified, pulse field gradient-enhanced inverse-detected HOESY pulse sequence for reduction oft1 spectral artifacts
journal, January 2002


Elucidation of the Solution Structures of Transition Metal Complex Ion Pairs by NOE NMR Experiments
journal, December 2002


1H, 19F-HOESY and PGSE diffusion studies on ionic liquids: The effect of co-solvent on structure
journal, April 2006


Structural Organization and Transport Properties of Novel Pyrrolidinium-Based Ionic Liquids with Perfluoroalkyl Sulfonylimide Anions
journal, August 2009


Blending ionic liquids: how physico-chemical properties change
journal, January 2010


Intermolecular association and supramolecular structures of PNVF–LiPFN and PVP–LiPFN complexes in the aqueous phase
journal, January 2010


Application of fluorine NMR for structure identification of steroids: Application of fluorine NMR for structure identification of steroids
journal, March 2011


NMR Investigation of Imidazolium-Based Ionic Liquids and Their Aqueous Mixtures
journal, January 2012


Heteronuclear NOE Spectroscopy of Ionic Liquids
journal, October 2011


Differences in Ion Interactions for Isoelectronic Ionic Liquid Homologs
journal, April 2013


Pyrazolium- versus Imidazolium-Based Ionic Liquids: Structure, Dynamics and Physicochemical Properties
journal, January 2013


Nonpolar, Polar, and Associating Solutes in Ionic Liquids
journal, August 2006

  • Canongia Lopes, José N.; Costa Gomes, Margarida F.; Pádua, Agílio A. H.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 34
  • https://doi.org/10.1021/jp063603r

Lifetimes, spectra, and quenching of the excited states of polypyridine complexes of iron(II), ruthenium(II), and osmium(II)
journal, February 1980


Photochemistry of tris(2,2'-bipyridine)ruthenium(2+) ion
journal, September 1982


Photochemistry of tris(2,2'-bipyridine)ruthenium(2+) ion (Ru(bpy)32+). Solvent effects
journal, August 1983


Solution-Processable Electrochemiluminescent Ion Gels for Flexible, Low-Voltage, Emissive Displays on Plastic
journal, February 2014


Elucidation of cross relaxation in liquids by two-dimensional N.M.R. spectroscopy
journal, January 2002


Structure of molten 1,3-dimethylimidazolium chloride using neutron diffraction
journal, January 2003


Understanding Ionic Liquids through Atomistic and Coarse-Grained Molecular Dynamics Simulations
journal, November 2007


Molecular Force Field for Ionic Liquids IV:  Trialkylimidazolium and Alkoxycarbonyl-Imidazolium Cations; Alkylsulfonate and Alkylsulfate Anions
journal, April 2008


Alkoxy Chain Effect on the Viscosity of a Quaternary Ammonium Ionic Liquid: Molecular Dynamics Simulations
journal, January 2009


Molecular Dynamics Simulations of the Liquid Surface of the Ionic Liquid 1-Hexyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)amide: Structure and Surface Tension
journal, October 2009


The effects of anion and cation substitution on the ultrafast solvent dynamics of ionic liquids: A time-resolved optical Kerr-effect spectroscopic study
journal, July 2003


Correlation between Quasielastic Raman Scattering and Configurational Entropy in an Ionic Liquid
journal, May 2007


Effect of Cation Symmetry on the Morphology and Physicochemical Properties of Imidazolium Ionic Liquids
journal, May 2011


Solution Structure Investigation of Ru(II) Complex Ion Pairs:  Quantitative NOE Measurements and Determination of Average Interionic Distances
journal, November 2001


Cover Picture: Champagne and Fireworks: Angewandte Chemie Celebrates Its Birthday (Angew. Chem. Int. Ed. 1/2013)
journal, December 2012


Works referencing / citing this record:

Design Principles of Ionic Liquids for Transdermal Drug Delivery
journal, May 2019


On the measurement of intermolecular heteronuclear cross relaxation rates in ionic liquids
journal, January 2018