Premium
Hydrostatic Pressure on Toroidal Interaction and Propeller Chirality of Hexaarylbenzenes: Explicit Solvent Effects on Differential Volumes in Methylcyclohexane and Hexane
Author(s) -
Kosaka Tomoyo,
Iwai Satono,
Fukuhara Gaku,
Imai Yoshitane,
Mori Tadashi
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201804688
Subject(s) - methylcyclohexane , conformational isomerism , hydrostatic pressure , propeller , chirality (physics) , hexane , toroid , chemistry , solvent , chemical physics , computational chemistry , thermodynamics , physics , symmetry breaking , organic chemistry , molecule , chiral symmetry breaking , quantum mechanics , plasma , marine engineering , nambu–jona lasinio model , engineering , catalysis
A unique and effective interaction between the peripheral aromatic blades makes hexaarylbenzenes (HABs) attractive in fundamental research as well as for various applications such as molecular wires, sensors, and supramolecular assemblies. The chiroptical responses of HABs are susceptible to environmental factors such as solvent and temperature owing to the dynamic conformational transitions between the conformers. In this study, pressure dependence on the propeller chiral HABs in two different solvents was studied in detail. The effective differential volumes for two different equilibria were determined by quantitative analyses of CD spectra, affording very large differential volumes from the propeller to toroidal conformer (Δ V T‐C ) of +43 and +42 cm 3 mol −1 , for H2 and H6 , respectively, in methylcyclohexane. The value of H6 was further enhanced to +72 cm 3 mol −1 in hexane, the largest value for the typical unimolecular conformational change. Such a response of propeller chirality in HABs is expedient in designing more advanced piezo‐sensitive materials.