Synthesis and photochromism of two new 1,2-bis(thiazolyl)perfluorocyclopentenes with chelating sites

Abstract

Two new dithiazolylethenes, 1a {1,2-bis[5′-methyl-2′-(2′′-pyridyl)thiazolyl]perfluorocyclopentene} and 2a {1,2-bis[4′-methyl-2′-(2′′-pyridyl)thiazolyl]perfluorocyclopentene}, have been synthesized. Their photochromic behavior has been fully investigated in solution as well as in the crystalline phase. They display both fatigue-resistant and thermally irreversible photochromic reactions, with more than 80% of the closed-ring forms (1b and 2b, respectively) in the photo-stationary state. Upon UV irradiation, a colorless solution of 1a turns purple while the yellow color of a 2a solution becomes more intense. Such marked differences in their electronic absorption spectra are reproduced by DFT calculations. Finally, although structurally closely related, only 1a shows photochromism in the crystalline phase whereas 2a displays reversible photo-modulation of fluorescence in solution.