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Inter- and intramolecular interactions in imidazolium protic ionic liquids.

Anastasia Maria Moschovi1, Vassileios Dracopoulos, Vladimiros Nikolakis

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The study investigates how alkyl chain length affects interactions in protic ionic liquids (PILs). Longer chains increase van der Waals forces, impacting melting points and glass transitions.

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Area of Science:

  • Materials Science
  • Physical Chemistry

Background:

  • Protic ionic liquids (PILs) are salts that are liquid at room temperature.
  • Understanding the interactions within PILs is crucial for their application.

Purpose of the Study:

  • To investigate the effect of alkyl chain length on the interactions in imidazolium bis(trifluoromethanesulfonyl)imide PILs.
  • To correlate these interactions with physical properties like melting point and glass transition temperature.

Main Methods:

  • Vibrational spectroscopy (FT-IR/ATR and FT-Raman) was used to study molecular interactions.
  • Differential scanning calorimetry (DSC) was employed to determine thermal properties.

Main Results:

  • For short alkyl chains (n < 3), intramolecular induction effects dominate.
  • For longer chains (n > 3), van der Waals and π-π interactions become significant, lowering melting points and increasing glass transition temperatures.
  • Anion conformational isomerism (ΔHeq) indicates the predominant interaction type.

Conclusions:

  • Alkyl chain length is a key factor controlling interactions in these PILs.
  • The balance of interactions (Coulombic, hydrogen bonding, van der Waals) dictates the material's properties.
  • Anion conformation serves as a reliable indicator of these interactions.