Photoprocesses of coordination compounds and dyes in solution and nanoporous materials: Evolution from milliseconds to femtoseconds #

The photoredox reactions of cobalt(III), nickel(II) complexes and organic dyes are reviewed with particular emphasis on using flash photolysis methods to identify the transients in the time scale from milliseconds to subpicoseconds. The excitation flash radiation initially was limited to flash lamps with a time resolution to study the decay of the excited states and the fast reactions of photo produced transients in milliseconds and microseconds. Some of the photolysis reactions investigated provide details in real time including the thermal reactions of molecular oxygen with cobalt(II) amine systems and the cobalt (III) alkyl complex formation on photolysis of cobalt(III) aminoacid complexes. Photoredox reactions of thiazine and safranine dyes are investigated using time resolved absorption and emission techniques in solution and on encapsulation in micro and mesoporous host materials. Picosecond and femtosecond diffuse reflectance fluorescence investigations in the porous solid host materials show intramolecular proton transfer reactions of the dyes and deprotonation of the dyes in the excited states. Photosensitization of nanoparticles of semiconductors, anatase TiO2 and ZnO by the excited states of dyes in meso and microporous silicate hosts is investigated using pico and femtosecond fluorescence and transient absorptions techniques and the results are reviewed.