A New Structure–Magnetism Relationship for Face‐Sharing Transition‐Metal Complexes with d³–d³ Electronic Configuration

A through‐space interaction and not superexchange of the bridging ligands explains the antiferromagnetic coupling in dinuclear face‐sharing octahedral complexes with d 3 ‐d 3 electronic configuration. The metal‐metal distance is the only relevant structural parameter for the spin‐exchange coupling constants of a series of V , Cr , and Mn complexes.