The ground- and excited-state properties of a series of [ReCl(CO)3(dppz)] complexes with substituted donor groups were investigated. Alteration of donor-acceptor communication through modulation of torsional angle and the number and nature of the donor substituents allowed the effects on the photophysical properties to be characterized though both computational and spectroscopic techniques, including time-dependent density functional theory and resonance Raman and time-resolved infrared spectroscopy. The ground-state optical properties show significant variation as a result of donor group modulation, with an increased angle between the donor and acceptor blue-shifting and depleting the intensity of the lowest-energy transition, which is consistently intraligand charge transfer (ILCT) in nature. However, across all complexes studied there was minimal perturbation to the excited-state properties and dynamics. Three excited states on the picosecond, nanosecond, and microsecond time scales were observed in all cases, corresponding to 1ILCT, 3ππ*, and 3ILCT, respectively.