INQUIMAE   12526
INSTITUTO DE QUIMICA, FISICA DE LOS MATERIALES, MEDIOAMBIENTE Y ENERGIA
Unidad Ejecutora - UE
artículos
Título:
The mechanism of the photochromic transformation of spirorhodamines
Autor/es:
HUGO MONTENEGRO, MATÍAS DI PAOLO, DAIANA CAPDEVILA, PEDRO F. ARAMENDÍA AND MARIANO L. BOSSI
Revista:
Photochemical and Photobiological Sciences
Editorial:
ROYAL SOC CHEMISTRY
Referencias:
Lugar: CAMBRIDGE; Año: 2012 vol. 11 p. 1081 - 1081
ISSN:
1474-905X
Resumen:
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.