A number of rhenium complexes with binaphthyridine and biquinoline ligands have been synthesized and studied. These are [Re(L)(CO)(3)Cl] where L = 3,3'-dimethylene-2,2'-bi-1,8-naphthyridine (dbn), 2,2'-bi-1,8-naphthyridine (bn), 3,3'-dimethylene-2,2'-biquinoline (dbq), and 3,3'-dimethyl-2,2'-biquinoline (diq). This series represents ligands in which the electronic properties and steric preferences are tuned. These complexes are modeled using density functional theory (DFT). An analysis of the resonance Raman spectra for these complexes, in concert with the vibrational assignments, reveals that the accepting molecular orbital (MO) in the metal-to-ligand charge transfer (MLCT) transition is the LUMO and causes bonding changes at the interring section of the ligand. The electronic absorption spectroelectrochemistry for the reduced complexes of [Re(dbn)(CO)(3)Cl], [Re(dbq)(CO)(3)Cl], and [Re(diq)(CO)(3)Cl] suggest that the singly occupied MO is delocalized over the entire ligand structure despite the nonplanar nature of the diq ligand in [Re(diq)(CO)(3)Cl]. The IR spectroelectrochemistry for [Re(dbn)(CO)(3)Cl], [Re(dbq)(CO)(3)Cl], and [Re(bn)(CO)(3)Cl] reveal that reduction lowers the CO ligand vibrational frequencies to a similar extent in all three complexes. The substitution of naphthyridine for quinoline has little effect on the nature of the singly occupied MO. These data are supported by DFT calculations on the reduced complexes, which reveal that the ligands are flattened out by reduction: This may explain the similarity in the properties of the reduced complexes.