Interligand electron transfer and transition state dynamics in Ru(II)trisbipyridine

The interligand electron transfer (ILET) dynamics in the excited metal-to-ligand charge transfer state of RuIItrisbipyridine have been studied using picosecond time-resolved absorption polarization spectroscopy. The ILET dynamics have been studied in several solvents with widely varying relaxation times, and over the temperature range of −85 °C to room temperature. The solvents studied include acetonitrile, propanol, ethylene glycol, and glycerol. The results show that ILET is relatively fast in acetonitrile (∼47 ps), slower and nonexponential in propanol and ethylene glycol (∼30–200 ps), and fast in glycerol (∼30 ps). The glycerol results are roughly temperature independent. These results can be understood in terms of a model in which photoexcitation places the system near the ILET transition state and solvent relaxation competes with ILET in the nascent distribution. Following solvent relaxation a slower, steady state (probably transition state theory) rate is obtained.