The ground and excited state photophysical properties of a series of fac-[Re(L)(CO)(3)(alpha-diimine)](n+) complexes, where L = Br-, Cl-, 4-dimethylaminopyridine (dmap) and pyridine (py) have been extensively studied utilizing numerous electronic and vibrational spectroscopic techniques in conjunction with a suite of quantum chemical methods. The a-diimine ligand consists of 1,10-phenanthroline with the highly electron donating triphenylamine (TPA) appended in the S position. This gives rise to intraligand charge transfer (ILCT) states lying lower in energy than the conventional metal-to-ligand charge transfer (MLCT) state, the energies of which are red and blue shifted, respectively, as the ancillary ligand, L becomes more electron withdrawing. The emitting state is (ILCT)-I-3 in nature for all complexes studied, characterized through transient absorption and emission, transient resonance Raman (TR2), time-resolved infrared (TRIR) spectroscopy and TDDFT calculations. Systematic modulation of the ancillary ligand causes unanticipated variation in the (ILCT)-I-3 lifetime by 2 orders of magnitude, ranging from 6.0 mu s for L = Br- to 27 ns for L = py, without altering the nature of the excited state formed or the relative order of the other CT states present. Temperature dependent lifetime measurements and quantum chemical calculations provide no clear indication of close lying deactivating states, MO switching, contributions from a halide-to-ligand charge transfer (XLCT) state or dramatic changes in spin-orbit coupling. It appears that the influence of the ancillary ligand on the excited state lifetime could be explained in terms of energy gap law, in which there is a correlation between ln(km) and Eem with a slope of -21.4 eV(-1) for the (ILCT)-I-3 emission.