Three intersecting {V} rings: {VSb}, an ultra-large polyoxovanadate cluster shell.

[VIV30SbIII8O78]12-, currently the largest known antimonato-polyoxovanadate (Sb-POV), features three perpendicular, intersecting 12-membered rings of edge-sharing O4V[double bond, length as m-dash]O square pyramids. While in two rings the apices of all O4V[double bond, length as m-dash]O pyramids point outwards, four apices of the third ring are directed into the cavity of the cluster shell, a concave structural motif not previously observed in polyoxovanadate chemistry. SbIII centers cap the eight niches defined by the octands of the {V30O78} cluster shell, resulting in discrete trigonal pyramidal SbO3 units, a second unprecedented feature. Within the resulting spin topology with numerous local geometrically frustrated motifs, the 30 spin-1/2 sites couple antiferromagnetically via a complex set of exchange pathways.