In order to understand and predict structural, redox, magnetic, and optical properties of more complex and potentially mesogenic electroactive compounds such as [Co^III(L^t-BuLC)₂]ClO₄ (1), five archetypical complexes of general formula [Co^III(L^RA)₂]ClO₄, where R = H (2), tert-butyl (3), methoxy (4), nitro (5), and chloro (6), were obtained and studied by means of several spectrometric, spectroscopic, and electrochemical methods. The complexes 2, 4, and 6 were characterized by single-crystal X-ray diffraction, and show the metal center in an approximate D_2h symmetry. Experimental results support the fact that the electron donating or withdrawing nature of the phenolate-appended substituents changes dramatically the redox and spectroscopic properties of these compounds. The 3d⁶ electronic configuration of the metal ion dominates the overall geometry adopted by these compounds with the phenolate rings occupying trans positions to one another. Formation of phenoxyl radicals has been observed for 1, 3, and 6, but irreversible ligand oxidation takes place upon bulk electrolysis. These data were compared to detailed B3LYP/6-31G (d)-level computational calculations and have been used to account for the results observed. A comparison between compound 1 and archetype 3, validates the approach of using archetypical models to study metal-containing soft materials.