title: Efficient oxidative cycloreversion reaction of photochromic dithiazolythiazole.
abstract: Electrochemical response of photochromic tearylenes was surveyed by means of cyclic voltammetry, DFT calculations, and spectroelectrochemistry. 4,5-Bis(2-phenyl-5-methylthiazolyl)-2-phenylthiazole was found to show electrochemical oxidative ring-cycloreversion reaction. The net current efficiency of the cycloreversion reaction under constant potential electrolysis was as high as 900%, which is ascribed to an electrochemical local-cell mechanism and a chain reaction mechanism. Electron transfer stopped-flow study using a chemical oxidant successfully identified radical cation intermediates of both closed- and open-ring isomers, involved in the oxidative cycloreversion process. The significantly long-lived radical cation of open-ring isomer with the lifetime of 33 s takes part in the indirect electron transfer process from the neutral closed-ring isomer to the radical cation of open-ring isomer in the chain reaction manner.
authors.affiliation: Graduate School of Materials Science, Nara Institute of Science and Technology, NAIST, Ikoma, Nara 630-0192, Japan.
authors.forename: Takuya
authors.initials: T
authors.lastname: Nakashima
authors.forename: Yoshiyuki
authors.initials: Y
authors.lastname: Kajiki
authors.forename: Sayo
authors.initials: S
authors.lastname: Fukumoto
authors.forename: Maki
authors.initials: M
authors.lastname: Taguchi
authors.forename: Satoshi
authors.initials: S
authors.lastname: Nagao
authors.forename: Shun
authors.initials: S
authors.lastname: Hirota
authors.forename: Tsuyoshi
authors.initials: T
authors.lastname: Kawai