Login / Signup

Dynamics of Meso-Chiral Interconversion in a Butterfly-Shape Overcrowded Alkene Rotor Tunable by Solvent Properties.

Kalathil K KarthaAtsuro TakaiZdeněk FuteraJan LabutaMasayuki Takeuchi
Published in: Angewandte Chemie (International ed. in English) (2021)
Elucidation of dynamics of molecular rotational motion is an essential part and challenging area of research. We demonstrate reversible diastereomeric interconversion of a molecular rotor composed of overcrowded butterfly-shape alkene (FDF). Its inherent dual rotatory motion (two rotors, one stator) with interconversion between two diastereomers, chiral trans-FDF and meso cis-FDF forms, has been examined in detail upon varying temperatures and solvents. The free energy profile of 180° revolution of one rotor part has a bimodal shape with unevenly positioned maxima (transition states). FDF in aromatic solvents adopts preferentially meso cis-conformation, while in non-aromatic solvents a chiral trans-conformation is more abundant owing to the solvent interactions with peripheral hexyl chains (solvophobic effect). Moderate correlations between the trans-FDF/cis-FDF ratio and solvent parameters, such as refractive index, polarizability, and viscosity were found.
Keyphrases
  • ionic liquid
  • molecular dynamics simulations
  • amino acid
  • crystal structure
  • high speed
  • single molecule
  • high intensity
  • mass spectrometry
  • quantum dots
  • chemotherapy induced
  • light emitting