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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.

Small, beautiful and magnetically exotic: {V4W2}- and {V4W4}-type polyoxometalates

Small, beautiful and magnetically exotic: {V₄W₂}- and {V₄W₄}-type polyoxometalates