Herve- and Krebs-Type Magnetic Polyoxometalate Dimers

Lacunary polyoxometalates (POMs) are negatively charged metal-oxo clusters, formally obtained from plenary topologies via fragment removal. Owing to the fragment removal, the lacunary POMs archetypes are rich in nucleophilic terminal oxo ligands, making them suitable for post-synthetic coordination with various heterometals. Trilacunary heteropolytungstates (hetero-POTs) based on bowl-shaped {W9O30} framework incorporating a central lone-pair containing {XO3} hetergroup (X = As-III, Sb-III, and Bi-III) function as all-inorganic scaffolds that in the presence of d-block metal cations typically construct sandwich-like dimers of Herve and/or Krebs. Herein we review the preparative approaches, as well as compositional and magnetic versatility of the constructed Herve- and Krebs-type dimers and discuss prospective uses as POMtronics.

Automated summary

Lacunary polyoxometalates are negatively charged metal-oxo clusters obtained by removing fragments from plenary topologies. They have nucleophilic terminal oxo ligands and can coordinate with various heterometals. Trilacunary heteropolytungstates based on a bowl-shaped framework can construct sandwich-like dimers known as Herve and Krebs-type in the presence of d-block metal cations.