Covalent Co–O–V and Sb–N Bonds Enable Polyoxovanadate Charge Control

[Image: see text] The formation of [{Co(II)(teta)(2)}{Co(II)(2)(tren)(teta)(2)}V(IV)(15)Sb(III)(6)O(42)(H(2)O)]·ca.9H(2)O [teta = triethylenetetraamine; tren = tris(2-aminoethyl)amine] illustrates a strategy toward reducing the molecular charge of polyoxovanadates, a key challenge in their use as components in single-molecule electronics. Here, a V–O–Co bond to a binuclear Co(2+)-centered complex and a Sb–N bond to the terminal N atom of a teta ligand of a mononuclear Co(2+) complex allow for full charge compensation of the archetypal molecular magnet [V(15)Sb(6)O(42)(H(2)O)](6–). Density functional theory based electron localization function analysis demonstrates that the Sb–N bond has an electron density similar to that of a Sb–O bond. Magnetic exchange coupling between the V(IV) and Co(II) spin centers mediated via the Sb–N bridge is comparably weakly antiferromagnetic.