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This report describes an isostructural series of dinuclear iron, cobalt, and nickel complexes bound by a redox-active 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, electrochemistry, 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 [( 3 PDI 2 )Fe 2 (PMe 3 ) 2 (μ-Cl)](OTf) and [( 3 PDI 2 )Co 2 (PMe 3 ) 2 (μ-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 [( 3 PDI 2 )Co 2 (PMe 3 ) 2 (μ-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 σ* orbital, which was found to be heavily mixed with the redox-active manifold of the 3 PDI 2 ligand. A similar trend was observed in the 37 and 38 e - dinickel complexes [( 3 PDI 2 )Ni 2 (PMe 3 ) 2 (μ-Cl)](OTf) 2 and [( 3 PDI 2 )Ni 2 (PMe 3 ) 2 (μ-Cl)](OTf); however, their higher electron counts lead to high-spin ground states that result from occupation of a high-lying δ/δ* manifold with significant Ni-N PDI σ* 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.

Interdependent Metal–Metal Bonding and Ligand Redox-Activity in a Series of Dinuclear Macrocyclic Complexes of Iron, Cobalt, and Nickel