In situ ligand exchange-mediated 0D/1D transformation of a polyoxovanadate

Abstract

The antimonato-polyoxovanadate {Ni^II(en)₃}₃[V^IV₁₅Sb^III₆O₄₂(H₂O)]·ca.15H₂O was utilized as a synthon for the solvothermal in situ generation of the new compound {Ni^II(phen)₃}₂[{Ni^II(en)₂}V^IV₁₅Sb^III₆O₄₂(H₂O)]·19H₂O, a rearrangement induced by ligand metathesis. While in the precursor structure cations and anions are isolated, the solid-state structure of the product is characterized by 1D chains consisting of alternating [V₁₅Sb₆O₄₂(H₂O)]⁶⁻ cluster shells and [Ni(en)₂]²⁺ units covalently linked to neighboring clusters via terminal oxygen atoms. Water clusters composed of sixteen hydrogen-bonded H₂O molecules are located in void spaces of the structure. The magnetic properties indicate weak antiferromagnetic interactions of the bridging Ni²⁺ center and adjacent polyoxovanadate anions, as well as small magnetic anisotropy of the individual Ni²⁺ centers.