Abstract
A series of five organic donor-pi-bridge-acceptor (D-pi-A) sensitizers is investigated within the context of their photoinduced charge-transfer properties. Thereby, the focus is set on the impact of structural modifications of the molecular architecture on the pi-systems of the dyes. In particular, two different modes of systematic extension of the sensitizers' pi-systems, namely, (i) within the electron donating site and (ii) within the pi-bridge, are investigated by means of steady-state and time-resolved spectroscopic methods. The photophysical studies of the molecules in solution and as deposited on Al2O3 or TiO2 films reveal that different effects on the charge-transfer characteristics evolve dependent where - within the molecular structure - the modification of the pi-system is performed. Hence, pi-extension of the donor sites, for instance, leads to a strong red shift of the absorption features and a variation of light-harvesting properties. Modifying the pi-bridges results in a spatial decoupling of the HOMO and LUMO orbitals, which goes along with changes of the electronic coupling to TiO2. Furthermore, solution studies show that the electronic structure of the dyes governs their singlet excited-state features. As shown, the results obtained from these studies then allow important predictions about the deactivation of the excited states of these molecules adsorbed on TiO2. Finally, quantum chemical methods - among others, time-dependent density functional theory calculations - provide conclusive insight into the relationship between the electronic structure of the dyes and its impact on the photoinduced charge-transfer characteristics.