Hexagonal Supramolecular Assemblies Based on a RuII(DMSO)3‐ or OsII(DMSO)3‐Capped {HW9O33} Isopolyanion with Potassium Cations as Linkers1. Issue 10 (18th September 2012)

• Record Type: Journal Article
• Authors: Barats‐Damatov, Delina; Shimon, Linda J. W.; Neumann, Ronny
• Other Names: Kortz Ulrich sponsoringEditor.; Liu Tianbo sponsoringEditor.
• Is Part Of: European journal of inorganic chemistry. Issue 10/11(2013)
• Page Start: 1649
• Page End: 1653
• Publication Date: 2012-09-18
• Subjects: Polyoxometalates -- Tungsten -- Ruthenium -- Osmium -- X‐ray diffraction; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201200953
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: Crystallization of the {HW9 O33 } isopolyanion in the presence of M II (DMSO)4 Cl2 (where M = Ru, Os) and Na and K cations yielded one‐dimensional chains, {K[HW9 O33 M2 (C2 H6 SO)6 ] 6– } n . The {HW9 O33 } isopolyanion is capped by M II (DMSO)3 moieties, which are, in turn, linked by potassium cations. The chains for the Ru II ‐based compound show a prismatic coordination around the K + linker and {HW9 O33 } moieties that are eclipsed relative to each other along the chain, while the Os II ‐based compound has an octahedral coordination around the K + linker and {HW9 O33 } 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 II compound, channels are obtained by the arrangement of six {K[HW9 O33 Ru2 (C2 H6 SO)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[HW9 O33 Ru2 (C2 H6 SO)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[HW9 O33 Os2 (C2 H6 SO)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 {HW9 O33 } unit. Here, the {K[HW9 O33 Os2 (C2 H6 SO)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. Abstract : {HW9 O33 } isopolyanions were capped by M II (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.