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High-Contrast and Fast Photorheological Switching of a Twist-Bend Nematic Liquid Crystal
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Stepwise Conformational Disorder in an Ionic Plastic Crystal.

Letícia A Souza1, Thamires A Lima2, Vitor H Paschoal3

  • 1Laboratório de Espectroscopia Molecular, Departamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, 05508-000 São Paulo, São Paulo, Brazil.

The Journal of Physical Chemistry. B
|April 25, 2025
PubMed
Summary
This summary is machine-generated.

Structural changes in choline bis(trifluoromethanesulfonyl)imide during phase transitions were studied. The choline cation gains flexibility in the plastic crystal phase, while the NTf2 anion remains rigid until melting, revealing decoupled dynamics.

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Area of Science:

  • Physical Chemistry
  • Materials Science
  • Spectroscopy

Background:

  • Ionic liquids (ILs) exhibit unique phase transitions.
  • Understanding structural dynamics in ILs is crucial for their applications.
  • Choline bis(trifluoromethanesulfonyl)imide ([Chol][NTf2]) is a representative IL.

Purpose of the Study:

  • To investigate the structural changes and conformational dynamics of [Chol][NTf2] during phase transitions.
  • To correlate spectroscopic observations with differential scanning calorimetry (DSC) data.

Main Methods:

  • In situ Raman spectroscopy coupled with DSC measurements.
  • Analysis of vibrational modes to identify conformers ([Chol]: gauche/anti, [NTf2]: transoid/cisoid).
  • Low-frequency Raman and inelastic neutron scattering (INS).
  • Infrared spectroscopy to probe hydrogen bonding.

Main Results:

  • The low-temperature crystal phase contains gauche [Chol] and transoid [NTf2] conformers.
  • In the plastic crystal phase, [Chol] gains conformational flexibility, while [NTf2] remains conformationally rigid.
  • Decoupled conformational dynamics between [Chol] and [NTf2] were observed.
  • [NTf2] gains flexibility only upon melting.
  • A cation-cation hydrogen bond motif, present in the liquid, is already observed in the plastic crystal phase.

Conclusions:

  • The plastic crystal phase of [Chol][NTf2] exhibits distinct structural and dynamic properties compared to the low-temperature crystal and liquid phases.
  • The decoupling of conformational dynamics between the cation and anion is a key feature of the plastic crystal phase.
  • The early emergence of hydrogen bonding in the plastic crystal phase influences its properties.