Hexagonal Supramolecular Assemblies Based on a RuII(DMSO)3- or OsII(DMSO)3-Capped {HW9O33} Isopolyanion with Potassium Cations as Linkers

Crystallization of the {HW9O33} isopolyanion in the presence of MII(DMSO)4Cl2 (where M = Ru, Os) and Na and K cations yielded one‐dimensional chains, {K[HW9O33M2(C2H6SO)6]6–}n. The {HW9O33} isopolyanion is capped by MII(DMSO)3 moieties, which are, in turn, linked by potassium cations. The chains for the RuII‐based compound show a prismatic coordination around the K+ linker and {HW9O33} moieties that are eclipsed relative to each other along the chain, while the OsII‐based compound has an octahedral coordination around the K+ linker and {HW9O33} moieties that are staggered relative to each other along the chain. The three‐dimensional arrangement of the two compounds is quite different. For the RuII compound, channels are obtained by the arrangement of six {K[HW9O33Ru2(C2H6SO)6]6–}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[HW9O33Ru2(C2H6SO)6]6–}n. The channels have an approximate diameter of 8 Å and are occupied by layers of six sodium cations that form chair‐like hexagons with Na–Na interatomic distances of 2.807 Å. There are five water molecules that separate the layers of the Na+ cations. For the osmium compound, two different types of channels, defined by the arrangement three {K[HW9O33Os2(C2H6SO)6]6–}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 {HW9O33} unit. Here, the {K[HW9O33Os2(C2H6SO)6]6–}n chains are eclipsed relative to one another. Water molecules occupy one channel, while the other channel is occupied by K+ cations hexacoordinated to aqua ligands. The approximate diameter of the channels is 5.5 Å. {HW9O33} isopolyanions were capped by MII(DMSO)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 channels defined by six polymer chains with a diameter of ca. 8 Å, while for Os, two types of channels of ca. 5.5 Å were formed defined by three polymer chains.