Photochromic properties of cationic merocyanine dyes. Thermal stability of the spiropyran form produced by irradiation with visible light

Abstract

A series of novel cationic merocyanine dyes were prepared by condensation of 1,2,3,3-tetramethylindolium derivatives and 3-formyl-4H-1-benzothiopyran or -benzopyran derivatives, and their photochromic properties were investigated, especially focusing on the substituent effect in the indolium moiety. These dyes were converted into the spiropyran (SP) form so as to be colorless by irradiation with visible light, although, left under darkness, the colored merocyanine (MC) form was reproduced. The thermal coloration was affected by two factors: the substituent in the indolium moiety and the counter anion. An electron-donating substituent such as a methoxy group at the 5 position effectively retarded the thermal coloration, whereas an electron-withdrawing group such as a nitro group accelerated it. These substituent effects afforded good linearity for the Hammett rule with para σ parameters, indicating that decrease of the electron density in the indoline moiety of the SP form facilitated heterolytic cleavage of the bond between the spiro carbon and the oxygen of the pyran ring.