The mechanism of the photochromic transformation of spirorhodamines

HUGO MONTENEGRO; MATÍAS DI PAOLO; DAIANA CAPDEVILA; PEDRO F. ARAMENDÍA; MARIANO L. BOSSI

Photochemical and Photobiological Sciences

ROYAL SOC CHEMISTRY

Lugar: CAMBRIDGE; Año: 2012 vol. 11 p. 1081 - 1086

1474-905X

We investigate the equilibrium, kinetics, and mechanism of the photochromic transformation of a series of amido spirorhodamine compounds?differing in the nature of the substituents of the amido group and in the rhodamine chromophore?in ethanol at room temperature in the presence of trifluoroacetic acid. A proton participates in the equilibrium between the spiro form and the open rhodamine form. The relaxation times in the dark or under continuous irradiation show a linear dependence on the proton concentration. The slopes of these plots show a linear free energy relation with the equilibrium constant of the transformation. A mechanism involving reversible reaction steps between four states: the two thermodynamically stable isomers, a protonated spiro form, and a deprotonated open form, can account for the kinetic observations in the dark and under irradiation.