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At room temperature, the chair conformer of cyclohexane undergoes rapid ring flipping between two equivalent chair conformers at a rate of approximately 105 times per second. These two chair conformers are in equilibrium. The rapid ring flipping results in the interconversion of the axial proton to an equatorial proton and an equatorial to the axial proton. Such interconversions are too rapid and cannot be detected on the NMR timescale. Hence, the NMR spectrometer cannot distinguish between the...
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Nematic molecular core flexibility and chiral induction.

Tzu-Chieh Lin1, Ian R Nemitz, Christopher J McGrath

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Flexible liquid crystal cores enable electroclinic responses by compensating for imposed twist. Rigid cores diminish this effect, indicating core flexibility is key for measurable electroclinic effects in chiral environments.

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Area of Science:

  • Materials Science
  • Condensed Matter Physics
  • Physical Chemistry

Background:

  • Electroclinic effect involves electric field-induced director rotation in chiral liquid crystals.
  • Achiral liquid crystals can exhibit chiral behavior in specific environments.
  • Understanding molecular structure-property relationships is crucial for designing advanced materials.

Purpose of the Study:

  • To investigate the electroclinic response in achiral liquid crystals with an imposed helical director profile.
  • To determine the influence of molecular core flexibility and chirality on the electroclinic effect.
  • To elucidate the mechanism underlying electroclinic responses in liquid crystal systems.

Main Methods:

  • Electroclinic measurements were performed on configurationally achiral liquid crystals.
  • An electric field was applied to induce director rotation in the presence of an imposed helical director profile.
  • Varying concentrations of flexible and rigid core mesogens and chiral dopants were studied.

Main Results:

  • A flexible phenyl benzoate core mesogen showed a measurable electroclinic response in the nematic phase.
  • Mixing with rigid core mesogens (fluorenone) or chiral dopants (2,2'-spirobiindan-1,1'-dione) significantly reduced the electroclinic response.
  • The electroclinic response diminished towards zero with increasing concentrations of rigid or chiral additives.

Conclusions:

  • The flexibility of the liquid crystal core is essential for observing the electroclinic effect.
  • Molecular deracemization to compensate for elastic energy cost of twist is the primary mechanism.
  • Structural design of liquid crystals can be tailored to control electroclinic properties.