Hybrid Polyoxovanadates: Anion-Influenced Formation of Nanoscopic Cages and Supramolecular Assemblies of Asymmetric Clusters

Two novel hybrid polyoxovanadates that are functionalized by (4-aminophenyl)­arsonic acid ligands form upon the reduction of vanadates­(V) in aqueous systems, whereby the underlying condensation reactions are influenced by the nature of the employed acid. In the presence of Cl– ions that derive from hydrochloric acid, a tetradecanuclear cage structure [VIV14O16(OH)8-­(O3AsC6H4-4-NH2)10]4–, whose cavity contains stabilizing halide ions and water molecules, is obtained. When nitric acid is used, a decanuclear [V10O18(O3AsC6H4-4-NH2)7(DMF)2]5– cluster can be isolated. The latter organizes into a hexagonal packing arrangement in the solid state.