What is the difference between the dynamics of anion- and keto-type of photochromic salicylaldehyde azine?

The normal and anion structures of salicylaldehyde azine (SAA) in solvents of different viscosities and polarities have been studied by means of femto- to nanosecond time-resolved emission techniques. In the normal form, an excited-state intramolecular proton-transfer (ESIPT) reaction takes place with a time constant shorter than 80 fs to produce an excited keto-type tautomer in which intramolecular-vibrational energy redistribution and vibrational cooling occur in 100 fs to 2 ps. The viscosity-dependent emission decay in the red part of the spectrum with 5-11 ps reflects a twisting motion leading to rotamers of these keto-type structures, most probably of (n, pi*) nature. For the anion type, the viscosity dependent rise-times (3 to 400 ps) at the red part of the emission, and the wavelength-dependent fluorescence lifetimes (20 to 1100 ps) indicate a stepwise formation of different conformers of the anions. The results reported here should be relevant to a better understanding of the photobehaviour of photochromic compounds and charged chromophores in biological systems.