title: Metastable liquid crystal as time-responsive reaction medium: aging-induced dual enantioselective control.
abstract: 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.
authors.affiliation: RIKEN Center for Emergent Matter Science, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan. y-ishida@riken.jp
authors.forename: Yasuhiro
authors.initials: Y
authors.lastname: Ishida
authors.forename: Yuki
authors.initials: Y
authors.lastname: Matsuoka
authors.forename: Yukiko
authors.initials: Y
authors.lastname: Kai
authors.forename: Kuniyo
authors.initials: K
authors.lastname: Yamada
authors.forename: Kenta
authors.initials: K
authors.lastname: Nakagawa
authors.forename: Toru
authors.initials: T
authors.lastname: Asahi
authors.forename: Kazuhiko
authors.initials: K
authors.lastname: Saigo