High Nuclearity Antimonato-Polyoxovanadate Cluster {V15 Sb6 O42 } as a Synthon for the Solvothermal in situ Generation of α- and β-{V14 Sb8 O42 } Isomers.

Abstract

New heteroatom polyoxovanadates (POVs) were synthesized by applying a water-soluble high-nuclearity cluster as new synthon. The [V15 Sb6 O42 ](6-) cluster shell exhibiting D3 symmetry was in situ transformed into completely different cluster shells, namely, the α-[V14 Sb8 O42 ](4-) isomer with D2d and the β-[V14 Sb8 O42 ](4-) isomer with D2h symmetry. The solvothermal reaction of {Ni(en)3 }3 [V15 Sb6 O42 (H2 O)x ]⋅15 H2 O (x=0 or 1; en=ethylenediamine) in water led to the crystallization of [{Ni(en)2 }2 V14 Sb8 O42 ]⋅5.5 H2 O containing the β-isomer. The addition of [Ni(phen)3 ](ClO4 )2 ⋅0.5 H2 O (phen=1,10-phenanthroline) to the reaction slurry gave the new compound {Ni(phen)3 }2 [V14 Sb8 O42 ]⋅phen⋅12 H2 O with the α-isomer. Both transformation reactions are complex due the change of symmetry, the chemical composition, and rearrangement of the VO5 square pyramids and Sb2 O5 handle-like moieties.