Metastable Liquid Crystal as Time-Responsive Reaction Medium: Aging-Induced Dual Enantioselective Control

Yasuhiro Ishida *†‡, Yuki Matsuoka ‡, Yukiko Kai §, Kuniyo Yamada †, Kenta Nakagawa , Toru Asahi , and Kazuhiko Saigo #

A metastable liquid crystal (LC) was found to serve as a time-responsive reaction medium, in which the enantioselectivity of a photoreaction was perfectly switched through isothermal annealing of the reaction system. When the LC salt of an enantiopure amine with a photoreactive acid was irradiated with UV/vis light, in situ photodimerization of the acid moiety proceeded smoothly to afford the (+)-isomer of the photodimer with high enantioselectivity (+86% ee). In contrast, photoirradiation of an aged sample, isothermally annealed for 20 h, gave predominantly the (−)-isomer (−94% ee). Systematic studies revealed that the reversal in selectivity originated from metastability of the LC system, which gradually transformed into a crystalline phase during annealing. This finding demonstrates the potential use of metastable aggregates as dynamic time-responsive media, reminiscent of biological systems.