The ligand 2,3,8,9,14,15-hexa(octyl-thioether)-5,6,11,12,17,18-hexaazatrinaphthalene (HATN-(SOct)6) and its mono-, bi-, and trinuclear Re(CO)3Cl complexes are reported. These are characterized by (1)H NMR spectroscopy and electrochemistry, and show broad, intense absorption across the visible wavelength region. Using time-dependent density functional theory (TD-DFT) calculations and resonance Raman spectroscopy these absorption bands are shown to be π → π*, MLCT, ILCT(sulfur → HATN), or mixed MLCT/ILCT in nature. Time-resolved infrared spectroscopy is used to probe structural changes and dynamics on short time scales and supports the assignment of a mixed MLCT/ILCT state in which both sulfur groups and one metal center act as electron donors to the HATN core.