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      The mechanism of the photochromic transformation of spirorhodamines.

      Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology
      Royal Society of Chemistry (RSC)

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          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.

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          Journal
          22534959
          10.1039/c2pp05402g

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