A series of dinuclear cobalt complexes of general formula [Co(Me(n)tpa)(diox-S-diox)Co(Me(n)tpa)]-(PF6)(2)center dot MeOH (n = 0, 2, 3) was prepared through the synthesis of the bis-bidentate ligand 6,6'-((1,4-phenylenebis(methylene))bis(sulfanediyl))bis(3,5-di-tert-butyl-benzene-1,2-diol) (diox-S-diox). The ancillary ligands Me(n)tpa are obtained by the tripodal tris(2-pyridylmethyl)amine (tpa) ligand through successive introduction of methyl groups into the 6 position of the pyridine moieties. As expected, the steric hindrance induced by this substitution modulates the redox properties of the metal acceptor, determining the charge distribution of the metal-dioxolene adduct at room temperature. Magnetic measurements and X-ray photoelectron and X-ray absorption spectroscopies indicate that the charge distributions low-spin-Co-III-catecholate and high-spin-Co-II-semiquinonate characterize the complexes formed by the tpa and Me(3)tpa tetradentate ligands, respectively. The complex formed by the Me(2)tpa ligand undergoes a thermal- and Light-induced interconversion of the two states, in agreement with the existence of a valence tautomeric equilibrium. All complexes were stable and behaved reproducibly under X-ray irradiation. This work points out a fast and simple chemical approach to structurally and electronically modify the catechol ring while leaving its coordination capabilities unaffected. These findings afford a robust chemical method to prepare sulfur-functionalized dioxolene ligands as new molecular bricks for chemical functionalization of noble metal surfaces with this class of molecular switches.