This report describes an isostructural series of dinuclear iron, cobalt, and nickel complexes bound by a redoxactive macrocyclic ligand. The series spans five redox levels (34-38 e(-)/cluster core), allowing for a detailed investigation into both the degree of metal-metal interaction and the extent of ligand-based redox-activity. Magnetometry, electro chemistry, UV-vis-NIR absorption spectroscopy, and crystallography were used in conjunction with DFT computational analyses to extract the electronic structures of the six homodinuclear complexes. The isoelectronic, 34 e(-) species [((PDI2)-P-3)Fe-2(PMe3)(2)(mu-Cl)](OTf) and [((PDI2)-P-3)Co-2(PMe3)(2)(mu-Cl](OTf)(3) exhibit metal-metal single bonds, with varying amounts of electron density delocalization into the ligand as a function of the effective nuclear charge of the metal ions. One-and two-electron reductions of [((PDI2)-P-3)Co-2(PMe3)(2) (mu-Cl)](OTf)(3) lead to isolable products, which show successive increases in both the Co-Co distances and the extent of reduction of the ligand manifold. This trend results from reduction of a Co-Co sigma* orbital, which was found to be heavily mixed with the redox-active manifold of the (PDI2)-P-3 ligand. A similar trend was observed in the 37 and 38 e(-) dinickel complexes [((PDI2)-P-3)Ni-2 (PMe3)(2) (mu-Cl)](OTf)(2) and [((PDI2)-P-3)Ni-2(PMe3)(2)(mu-Cl)](OTf); however, their higher electron counts lead to high-spin ground states that result from occupation of a high-lying delta/delta* manifold with significant Ni-N-PDI sigma* character. This change in ground state configuration reforms a M-M bonding interaction in the 37 e(-) complex, but formation of the 38 e(-) species again disrupts the M-M bond alongside the transfer of electron density to the ligand.