Intraligand Charge-Transfer Excited States in Re(I) Complexes with Donor-Substituted Dipyridophenazine Ligands

The donor-acceptor ligands 11-(4-diphenylaminophenyl) dipyrido [3,2-a: 2',3'-c]phenazine (dppz-PhNPh2) and 11-(4-dimethylaminophenyl)dipyrido[3,2-a:2',3'-c]-phenazine (dppz-PhNMe2), and their rhenium complexes, [Re(CO)(3)X] (X = Cl-, py, 4-dimethylaminopyridine (dmap)), are reported. Crystal structures of the two ligands were obtained. The optical properties of the ligands and complexes are dominated by intraligand charge transfer (ILCT) transitions from the amine to the dppz moieties with lambda(abs) = 463 nm (epsilon = 13 100 M-1 cm(-1)) for dppz-PhNMe2 and with lambda(abs) = 457 nm (epsilon = 16 900 M-1 cm(-1)) for dppz-PhNPh2. This assignment is supported by CAM-B3LYP TD-DFT calculations. These ligands are strongly emissive in organic solvents and, consistent with the ILCT character, show strong solvatochromic behavior. Lippert-Mataga plots of the data are linear and yield Delta mu values of 22 D for dppz-PhNPh2 and 20 D for dppz-PhNMe2. The rhenium(I) complexes are less emissive, and it is possible to measure resonance Raman spectra. These data show relative band intensities that are virtually unchanged from lambda(exc) = 351 to 532 nm, consistent with a single dominant transition in the visible region. Resonance Raman excitation profiles are solvent sensitive; these data are modeled using wavepacket theory yielding reorganization energies ranging from 1800 cm(-1) in toluene to 6900 cm(-1) in CH3CN. The excited state electronic absorption and infrared spectroscopy reveal the presence of dark excited states with nanosecond to microsecond lifetimes that are sensitive to the ancillary ligand on the rhenium. These dark states were assigned as phenazine-based (ILCT)-I-3 states by time-resolved infrared spectroscopy. Time-resolved infrared spectroscopy shows transient features in which Delta nu(CO) is approximately 7 cm(-1), consistent with a ligand-centered excited state. Evidence for two such states is seen in mid-infrared transient spectra.