Monitoring the intramolecular charge transfer process in the Z907 solar cell sensitizer: a transient Vis and IR spectroscopy and ab initio investigation

We have analyzed the excited state dynamics of the heteroleptic [(NCS)<inf>2</inf>Ru(bpy-(COOH)<inf>2</inf>)(bpy-(C<inf>6</inf>H<inf>13</inf>)<inf>2</inf>)] Z907 solar cell sensitizer in solution and when adsorbed onto thin TiO<inf>2</inf> films, by combining transient visible and infrared (IR) spectroscopies with ab initio Density Functional Theory (DFT) and Time-Dependent DFT (TDDFT) calculations. Upon excitation with ultra-short pulses in ethanol and dimethyl-sulphoxide solutions, the visible spectra show the appearance of a positive signal around 650 nm, within the instrumental time resolution (<100 fs), which in ethanol undergoes a red-shift in about 20 ps. Measurements in the IR indicate that, upon excitation, both the CN and CO marker bands, associated with the NCS and COOH groups, downshift in frequency, in response to intramolecular ligand + metal (Ru-NCS) to ligand' (bpy-COOH<inf>2</inf>) charge transfer (LML'CT). Vibrational cooling is observed in both solvents; in ethanol it is overtaken by the hydrogen bond dynamics. On the basis of DFT/TDDFT calculations, explicitly modeling the interaction of the NCS and COOH groups with solvent (ethanol) molecules, we rationalize the observed IR and visible spectral evolution as arising from the change in the hydrogen-bond network, which accompanies the transition to the lowest-energy triplet state. This interpretation provides a consistent explanation of what is also observed in the transient visible spectra. Transient IR measurements repeated for molecules adsorbed on TiO<inf>2</inf> and ZrO<inf>2</inf> films, allow us to identify the structural changes signaling the dye triplet excited state formation and evidence multiexponential electron injection rates into the semiconductor TiO<inf>2</inf> film.