Fast and Efficient Oxidative Cycloreversion Reaction of a π-Extended Photochromic Terarylene.
Chemistry
; 22(29): 10002-8, 2016 Jul 11.
Article
in En
| MEDLINE
| ID: mdl-27380748
ABSTRACT
We report herein a dramatic improvement in the kinetics and efficiency of an oxidative cycloreversion reaction of photochromic dithiazolylthiazoles. The cycloreversion reaction of a colored isomer of dithiazolylthiazole proceeds not only by photo-irradiation, but also through chemical oxidation with a net efficiency far exceeding 100 % owing to a chain reaction mechanism. By introducing aromatic groups on the reactive carbon atoms at the ends of a photoreactive 6π system in a dithiazolylthiazole, the net bleaching reaction rates were increased by up to 1300-fold, and turnover rates increased by two orders of magnitude. Based on a combination of classical kinetic analyses and DFT calculations, we attribute this improvement to acceleration of the rate-determining step to produce the active species in the chain-reaction oxidative cycloreversion.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
Chemistry
Journal subject:
QUIMICA
Year:
2016
Document type:
Article
Affiliation country:
Japan