The formation of [{CoII(teta)2}{CoII2(tren)(teta)2}VIV15SbIII6O42(H2O)]·ca.9H2O [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 Co2+-centered complex and a Sb–N bond to the terminal N atom of a teta ligand of a mononuclear Co2+ complex allow for full charge compensation of the archetypal molecular magnet [V15Sb6O42(H2O)]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 VIV and CoII spin centers mediated via the Sb–N bridge is comparably weakly antiferromagnetic.

Molecular metal oxides often adopt common structural frameworks (i.e. archetypes), many of them boasting impressive structural robustness and stability. However, the ability to adapt and to undergo transformations between different...

No abstract

Minimal-nuclearity vanadato-tungstate clusters in [{V(IV)(dien)}4WO14]·4H2O () and [{V(IV)(dien)}4WO20]·6H2O () feature cores of edge-sharing WO6 octahedra, surrounded by a ring of four vanadyl groups. Surprisingly, the V(iv) centers in both and are ferromagnetically coupled, in contrast to all other known vanadato-polyoxotungstates featuring the ubiquituos V-O-W-O-V exchange pathways.

No abstract