@article{cd50a8045def478e81e0dd488163fa70,
title = "Dynamics of Meso–Chiral Interconversion in a Butterfly-Shape Overcrowded Alkene Rotor Tunable by Solvent Properties",
abstract = "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.",
keywords = "chirality, conformation analysis, crowded alkenes, diastereomers, solvent effects",
author = "Kartha, {Kalathil K.} and Atsuro Takai and Zden{\v e}k Futera and Jan Labuta and Masayuki Takeuchi",
note = "Funding Information: We are grateful to Dr. Takeshi Yasuda (NIMS), Dr. Takashi Kajitani (Tokyo Tech.), and Prof. Takanori Fukushima (Tokyo Tech.) for their efforts on the physicochemical studies of in the solid states. Dr. Manas Bera (NIMS) is greatly acknowledged for his contribution in the initial stages of this work. This research was supported by KAKENHI Grant‐in‐Aid for Scientific Research (No. 19K05229 for J.L.); Innovative Areas “π‐System Figuration” Grant (No. 26102009 and No. 15K21721 for M.T.) from JSPS; Grant‐in‐Aid for Transformative Research Areas (A) “Condensed Conjugation” from MEXT (20H05868 for M.T.); and the MEXT “NIMS Molecule and Material Synthesis Platform” program. Z.F. is also grateful for computational resources supplied by project “e‐Infrastruktura CZ” (e‐INFRA LM2018140) provided within the program Projects of Large Research, Development, and Innovations Infrastructures. FDF Funding Information: We are grateful to Dr. Takeshi Yasuda (NIMS), Dr. Takashi Kajitani (Tokyo Tech.), and Prof. Takanori Fukushima (Tokyo Tech.) for their efforts on the physicochemical studies of FDF in the solid states. Dr. Manas Bera (NIMS) is greatly acknowledged for his contribution in the initial stages of this work. This research was supported by KAKENHI Grant-in-Aid for Scientific Research (No. 19K05229 for J.L.); Innovative Areas ??-System Figuration? Grant (No. 26102009 and No. 15K21721 for M.T.) from JSPS; Grant-in-Aid for Transformative Research Areas (A) ?Condensed Conjugation? from MEXT (20H05868 for M.T.); and the MEXT ?NIMS Molecule and Material Synthesis Platform? program. Z.F. is also grateful for computational resources supplied by project ?e-Infrastruktura CZ? (e-INFRA LM2018140) provided within the program Projects of Large Research, Development, and Innovations Infrastructures. Publisher Copyright: {\textcopyright} 2021 Wiley-VCH GmbH",
year = "2021",
month = jul,
day = "19",
doi = "10.1002/anie.202102719",
language = "English",
volume = "60",
pages = "16466--16471",
journal = "Angewandte Chemie - International Edition",
issn = "1433-7851",
publisher = "John Wiley and Sons Ltd",
number = "30",
}