The geometric and electronic structure of a doubly oxidized bimetallic Co complex containing two redox-active salen moieties connected via a 1,2-phenylene linker was investigated and compared to an oxidized monomeric analogue. Both complexes, namely, CoL1 and Co2L2, are oxidized to the mono- and dications, respectively, with AgSbF6 and characterized by X-ray crystallography for the monomer and by vis-NIR (NIR = near-infrared) spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, superconducting quantum interference device (SQUID) magnetometry, and density functional theory (DFT) calculations for both the monomer and dimer. Both complexes exhibit a water molecule coordinated in the apical position upon oxidation. [CoL1-H2O](+) displays a broad NIR band at 8500 cm(-1) (8400 M-1 cm(-1)), which is consistent with recent reports on oxidized Co salen complexes (Kochem, A. et al., Inorg. Chem., 2012, 51, 1055710571 and Kurahashi, T. et al., Inorg. Chem., 2013, 52, 39083919). DFT calculations predict a triplet ground state with significant ligand and metal contributions to the singularly occupied molecular orbitals. The majority (similar to 75%) of the total spin density is localized on the metal, highlighting both high-spin Co(III) and Co(II)L-center dot character in the electronic ground state. Further oxidation of CoL1 to the dication affords a low-spin Co(III) phenoxyl radical species. The NIR features for [Co2L2-2H(2)O](2+) at 8600 cm(-1) (17 800 M-1 cm(-1)) are doubly intense in comparison to [CoL1-H2O](+) owing to the description of [Co2L2-2H(2)O](2+) as two non-interacting oxidized Co salen complexes bound via the central phenylene linker. Interestingly, TD-DFT calculations predict two electronic transitions that are 353 cm(-1) apart. The NIR spectrum of the analogous Ni complex, [Ni2L2](2+), exhibits two intense transitions (4890 cm(-1)/26 500 M-1 cm(-1) and 4200 cm(-1)/21 200 M-1 cm(-1)) due to exciton coupling in the excited state. Only one broad band is observed in the NIR spectrum for [Co2L2-2H(2)O](2+) as a result of the contracted donor and acceptor orbitals and overall CT character.