Effects of C(2) Methylation on Thermal Behavior and Interionic Interactions in Imidazolium-Based Ionic Liquids with Highly Symmetric Anions

Boumediene Haddad, Johannes Kiefer*, Houari Brahim, El-habib Belarbi, Didier Villemin, Serge Bresson, Ouissam Abbas, Mustapha Rahmouni, Annalisa Paolone, Oriele Palumbo

*Corresponding author for this work

Research output: Contribution to journalArticle

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Abstract

The chemical and physical properties of imidazolium-based ionic liquids are determined by the interactions between the counter-ions. The C(2) position plays an important role in these interactions, as it represents the predominant site for interionic hydrogen bonding. This study shows that the directional hydrogen bonds between highly symmetrical anions (iodide, tetrafluoroborate, hexafluorophosphate) and the C(2)-H group of the 1-methyl-3-propylimidazolium cation determine the molecular and macroscopic behavior in terms of the thermal properties. Upon replacing the C(2) proton by a methyl group, the anion repositions itself at the C(4)/(5) moiety, where it forms a new hydrogen bond, apparently with only one of the two CH groups. In addition, the larger the anion is in diameter, the more likely it will establish further interactions with other parts of the cation, such as the propyl chain.

Original languageEnglish
Article number1043
Number of pages18
JournalApplied Sciences
Volume8
Issue number7
Early online date26 Jun 2018
DOIs
Publication statusPublished - Jul 2018

Keywords

  • hydrogen bonding
  • ionic liquid
  • imidazolium
  • vibrational spectroscopy
  • CH STRETCHING VIBRATIONS
  • 1-ETHYL-3-METHYLIMIDAZOLIUM BIS(TRIFLUOROMETHYLSULFONYL)IMIDE
  • ELECTRONIC-STRUCTURE
  • MOLECULAR-STRUCTURE
  • HYDROGEN-BONDS
  • INFRARED-SPECTRA
  • CATION-ANION
  • SPECTROSCOPY
  • RAMAN
  • PAIR

Cite this

Effects of C(2) Methylation on Thermal Behavior and Interionic Interactions in Imidazolium-Based Ionic Liquids with Highly Symmetric Anions. / Haddad, Boumediene; Kiefer, Johannes; Brahim, Houari; Belarbi, El-habib; Villemin, Didier; Bresson, Serge; Abbas, Ouissam; Rahmouni, Mustapha; Paolone, Annalisa; Palumbo, Oriele.

In: Applied Sciences, Vol. 8, No. 7, 1043, 07.2018.

Research output: Contribution to journalArticle

Haddad, B, Kiefer, J, Brahim, H, Belarbi, E, Villemin, D, Bresson, S, Abbas, O, Rahmouni, M, Paolone, A & Palumbo, O 2018, 'Effects of C(2) Methylation on Thermal Behavior and Interionic Interactions in Imidazolium-Based Ionic Liquids with Highly Symmetric Anions', Applied Sciences, vol. 8, no. 7, 1043. https://doi.org/10.3390/app8071043
Haddad, Boumediene ; Kiefer, Johannes ; Brahim, Houari ; Belarbi, El-habib ; Villemin, Didier ; Bresson, Serge ; Abbas, Ouissam ; Rahmouni, Mustapha ; Paolone, Annalisa ; Palumbo, Oriele. / Effects of C(2) Methylation on Thermal Behavior and Interionic Interactions in Imidazolium-Based Ionic Liquids with Highly Symmetric Anions. In: Applied Sciences. 2018 ; Vol. 8, No. 7.
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abstract = "The chemical and physical properties of imidazolium-based ionic liquids are determined by the interactions between the counter-ions. The C(2) position plays an important role in these interactions, as it represents the predominant site for interionic hydrogen bonding. This study shows that the directional hydrogen bonds between highly symmetrical anions (iodide, tetrafluoroborate, hexafluorophosphate) and the C(2)-H group of the 1-methyl-3-propylimidazolium cation determine the molecular and macroscopic behavior in terms of the thermal properties. Upon replacing the C(2) proton by a methyl group, the anion repositions itself at the C(4)/(5) moiety, where it forms a new hydrogen bond, apparently with only one of the two CH groups. In addition, the larger the anion is in diameter, the more likely it will establish further interactions with other parts of the cation, such as the propyl chain.",
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AB - The chemical and physical properties of imidazolium-based ionic liquids are determined by the interactions between the counter-ions. The C(2) position plays an important role in these interactions, as it represents the predominant site for interionic hydrogen bonding. This study shows that the directional hydrogen bonds between highly symmetrical anions (iodide, tetrafluoroborate, hexafluorophosphate) and the C(2)-H group of the 1-methyl-3-propylimidazolium cation determine the molecular and macroscopic behavior in terms of the thermal properties. Upon replacing the C(2) proton by a methyl group, the anion repositions itself at the C(4)/(5) moiety, where it forms a new hydrogen bond, apparently with only one of the two CH groups. In addition, the larger the anion is in diameter, the more likely it will establish further interactions with other parts of the cation, such as the propyl chain.

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