A series of sulfur-substituted dppz-based ligands and their Re(I)(CO)(3)Cl complexes are reported. The sulfur-substituted ligands and complexes show interesting electronic properties atypical of dppz-type systems. Substitution of dppz with thiocyanate (SCN) groups results in behavior typical of an electron withdrawing group. However, substitution of dppz with the electron donating trithiocarbonate (S2CS) or deca-alkylthioether (Sdec) groups confer intraligand charge-transfer (ICT) from the S adduct to the phenazine lowest unoccupied molecular orbital (LUMO). Upon complexation of the substituted dppz ligand to Re(CO)(3)Cl this ICT red-shifts and increases in intensity. Analysis of these observations using density functional theory (DFT) calculations and resonance Raman spectroscopy reveals that these transitions are a mixture of metal-to-ligand charge-transfer (MLCT) and S -> phenazine ICI in nature. The synthesized compounds are also characterized using H-1 NMR spectroscopy, IR spectroscopy, and electrochemistry. Single-crystal X-ray analysis was performed on dppz(SCN)(2) (C20H18N6S2 a = 8.780 angstrom, b = 9.792 angstrom, c=10.400 angstrom, alpha = 95.95 degrees, beta = 112.13 degrees, gamma = 95.38 degrees, triclinic, P (1) over bar, Z=2, R1 = 0.0306, wR2 = 0.0829.