Photophysical Processes Occurring in a Zn-phthalocyanine in Ethanol Solution and on TiO2 Nanostructures

The photophysics of 9(19),16(17),23(24)-tri-tert-butyl-2-[ethynyl-(4-carboxymethyl)phenyl] phthalocyaninatozinc(II) (ZnPc) in solution and adsorbed on TiO2 and ZrO2 nanoparticle films is characterized by stationary and time-resolved spectroscopies in the subpicosecond to nanosecond time interval. The comparison between the solution and the solid substrate data allows us to identify different pathways of the energy and electron relaxation. On the solid substrate, the presence of H-aggregates adds a further nonradiative deactivation channel competing with the charge injection into the Ti-2-conducting band, thus providing an explanation of the reduced efficiency of the charge transfer processes. The comparison between the kinetics recorded after excitation of the S-0-S-2 transition and those recorded after excitation of the S-0-S-1 transition provides an estimate of the internal conversion between S-2 and S-1 which occurs very efficiently and on an ultrafast (<50 fs) time scale. The ground-state recovery characterized by the decay of the bleaching band in the transient spectra slows down in TiO2 samples and is taken as evidence of the charge injection in this kind of sample.