Photostability and Spectral Properties of Fluorinated Fluoresceins and their Biarsenical Derivatives: A Combined Experimental and Theoretical Study

CARLA C. SPAGNUOLO; WALTER MASSAD; SANDRA MISKOSKI; GUILLERMO O. MENENDEZ; NORMAN A. GARCÍA; ELIZABETH A. JARES-ERIJMAN

PHOTOCHEMISTRY AND PHOTOBIOLOGY

WILEY-BLACKWELL PUBLISHING, INC

Año: 2009 vol. 85 p. 1082 - 1088

0031-8655

New fluorinated biarsenical derivatives with improved optical properties based on highly photostable analogs of fluorescein were recently introduced. The photophysical parameters of the triplet excited states as well as photosensitized oxidation reactions of these dyes were determined in order to investigate the influence of molecular structure on the exceptional photostability of these fluorophores. The lack of correspondence between triplet quantum yields and lifetimes with the photobleaching rates of some of the fluorophores of the series suggests that differential reactivities of the excited states with ground state oxygen accounts for the different photodegradation resistances. The UV–visible absorption and emission spectra of the fluorinated fluoresceins and their biarsenical derivatives were evaluated using a TD-DFT ⁄ BP86 ⁄ 6-31G** approach, taking bulk solvent effects into account by means of the polarizable continuum model. The calculated properties are in good agreement with experimental data. The S0 -> S1 vertical excitation energies in the gas phase and in water were obtained with the optimized geometries of the excited states. This type of calculation could be used in the rational design of new dyes.