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The mechanism of the photochromic transformation of spirorhodamines
- Source :
- Photochemical & Photobiological Sciences. 11:1081-1086
- Publication Year :
- 2012
- Publisher :
- Springer Science and Business Media LLC, 2012.
-
Abstract
- 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.
Details
- ISSN :
- 14749092 and 1474905X
- Volume :
- 11
- Database :
- OpenAIRE
- Journal :
- Photochemical & Photobiological Sciences
- Accession number :
- edsair.doi.dedup.....245ebad183dc4f6b2fe8ef55e0dd0e24