Journal of the Brazilian Chemical Society
On-line version ISSN 1678-4790
BENI, Alessandra et al. Optically induced valence tautomeric interconversion in cobalt dioxolene complexes. J. Braz. Chem. Soc. [online]. 2006, vol.17, n.8, pp. 1522-1533. ISSN 1678-4790. http://dx.doi.org/10.1590/S0103-50532006000800007.
The discovery that a number of cobalt-dioxolene complexes undergo photoswitchable behavior was reported in the recent past. This phenomenon is always associated with valence tautomeric interconversion processes involving low-spin cobalt(III) and high-spin cobalt(II) species. Herein is stressed the strong formal correlation existing between these processes and the LIESST (Light-Induced Excited Spin State Trapping) effect shown by several iron(II) complexes undergoing spin crossover interconversion. The dynamics of the relaxation of the photoinduced metastable species to the ground state is discussed in terms of non-adiabatic processes within the Jortner theory of radiationless multiphonon relaxation.
Keywords : valence tautomerism; redox isomerism; photochromism; photoinduction; photomagnetism; semiquinone; radical ligand.