Probing the excited states of Ru(II) complexes with dipyrido[2,3-a:3',2'-c]phenazine: a transient resonance raman spectroscopy and computational study

The lifetimes and transient resonance Raman spectra for Ru(II) complexes with the dipyrido[2,3-a:3',2'-c]phenazine (ppb) ligand and substituted analogues have been measured. The effect of altering the Ru(II) center ([Ru(CN)4]2- versus [Ru(bpy)2]2+), of the complex, on the excited-state lifetimes and spectra has been considered. For [Ru(bpy)2L]2+ complexes the excited-state lifetimes range from 124 to 600 ns in MeCN depending on the substituents on the ppb ligand. For the [Ru(CN)4L]2- complexes the lifetimes in H2O are approximately 5 ns. The transient resonance Raman spectra for the MLCT excited states of these complexes have been measured. The data are analyzed by comparison with the resonance Raman spectra of the electrochemically reduced [(PPh3)2Cu(mu-L*-)Cu(PPh3)2]+ complexes. The vibrational spectra of the complexes have been modeled using DFT methods. For experimental ground-state vibrational spectra of the complexes the data may be compared to calculated spectra of the ligand or metal complex. It is found that the mean absolute deviation between experimental and calculated frequencies is less for the calculation on the respective metal complexes than for the ligand. For the transient resonance Raman spectra of the complexes the observed vibrational bands may be compared with those of the calculated ligand radical anion, the reduced complex [Ru(CN)4L*-]3-, or the triplet state of the complex. In terms of a correlation with the observed transient RR spectra, calculations on the metal complex models offered no significant improvement compared to those based on the ligand radical anion alone. In all cases small structural changes are predicted on going from the ground to excited state.