Hexagonal Supramolecular Assemblies Based on a Ru super(II)(DMSO) sub(3)- or Os super(II)(DMSO) sub(3)-Cappe d {HW sub(9)O sub(33)} Isopolyanion with Potassium Cations as Linkers

Crystallization of the {HW sub(9)O sub(33)} isopolyanion in the presence of M super(II)(DMSO) sub(4)Cl sub(2) (where M = Ru, Os) and Na and K cations yielded one-dimensional chains, {K[HW sub(9)O sub(33)M sub( 2)(C sub(2)H sub(6)SO) sub(6)] super(6-)} sub(n) The {HW sub(9)O sub(33)} isopolyanion is capped by M super(II)(DMSO) sub(3) moieties, which are, in turn, linked by potassium cations. The chains for the Ru super(II)-based compound show a prismatic coordination around the K super(+) linker and {HW sub(9)O sub(33)} moieties that are eclipsed relative to each other along the chain, while the Os super(II)-based compound has an octahedral coordination around the K super(+) linker and {HW sub(9)O sub(33)} moieties that are staggered relative to each other along the chain. The three-dimensional arrangement of the two compounds is quite different. For the Ru super(II) compound, channels are obtained by the arrangement of six {K[HW sub(9)O sub(33)Ru sub(2)(C sub(2)H sub(6)SO) sub(6)] super(6-)} sub(n)chains along the c axis. The channel is stabilized by the binding of sodium cations, which interlock the chains through coordination of different oxygen atoms and leads to a tight staggered arrangement between the chains of {K[HW sub(9)O sub(33)Ru sub(2)(C sub(2)H sub(6)SO) sub(6)] super(6-)} sub(n) The channels have an approximate diameter of 8 Aa and are occupied by layers of six sodium cations that form chair-like hexagons with Na-Na interatomic distances of 2.807 Aa. There are five water molecules that separate the layers of the Na super(+) cations. For the osmium compound, two different types of channels, defined by the arrangement three {K[HW sub(9)O sub(33)Os sub(2)(C sub(2)H sub(6)SO) sub(6)] super(6-)} sub(n)chains, are formed. The channels are formed through interchain bonding through a bridge formed by connecting sodium atoms to the terminal atoms of the {HW sub(9)O sub(33)} unit. Here, the {K[HW sub(9)O sub(33)Os sub(2)(C sub(2)H sub(6)SO) sub(6)] super(6-)} sub(n)chains are eclipsed relative to one another. Water molecules occupy one channel, while the other channel is occupied by K super(+) cations hexacoordinated to aqua ligands. The approximate diameter of the channels is 5.5 Aa. {HW sub(9)O sub(33)} isopolyanions were capped by M super(II)(DMSO) sub(3) moieties (where M = Ru, Os), which were, in turn, linked by potassium cations to give polymer chains that were somewhat different for the Ru and Os analogues. For Ru, the 3D structures showed chann