Polyoxometalate Crown Ether Complexes with Supramolecular cations

POLYOXOMETALATE CROWN ETHER COMPLEXES WITH SUPRAMOLECULAR CATIONS 

In the isopolyanion [Mo Oig] (also known as a Lindqvist-type polyoxometalate anion), each Mo atom is surrounded by a distorted octahedron consisting of one central Oc, one terminal Ot, and four bridging Ob atoms (Fig. 29). In the crystal structure, the atypical trigonal bipyramidal TBP-[Cu(H20)5] ion is 

The trigonal bipyramidal coordination geometry around the Cu ion in [Cu(H20)5] species (Figs. 29 and 30) is decided by its participation in forming a supramolecular sandwich with two crown ethers that involves hydrogen 

In the crystal structure of [Cu(H20)5(Ci2H2406)2][Mo60ig], each sandwich is anchored (through C—H O hydrogen bonding interactions Fig. 29) 

Polyoxometalates also play an important role in the selection of a metal ion for its complete encapsulation in the cavity of a crown ether to form an unusual supramolecular cation structure. For example, the crown ethers (macrocyclic polyethers), generally, do not readily form complexes with first-row transition metals in their low oxidation states because such metal ions provide only soft coordination (acceptor) sites and crown ethers have hard donor atoms. Naturally, only a few first-row transition metal rown ether complexes had been structurally characterized in which a direct bond formation between a transition metal and the crown ether oxygen atoms became possible rare examples of this kind are offered by the smaller ring crown ethers (e.g., 15-crown-5 and 

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III. POLYOXOMETALATE CROWN ETHER COMPLEXES WITH SUPRAMOLECULAR CATIONS... 

Detailed discussions on supramolecular structures of giant polyoxometalate clusters have been reported by Muller and co-workers." " The number of ionic lattices formed from anionic POM clusters and organic cations-coordination complex cations resulting in supramolecular structures is substantial and literally more than hundreds of new compounds in this class appear annuallyIn this overview, the supramolecular features of POM-based systems will be discussed mainly under three headings (a) supramolecular features of polyoxometalate supported transition metal complexes, (b) polyoxometalate-crown ether complexes with supramolecular cations, and (c) supramolecular water clusters associated with polyoxometalates. 

Polyoxometalate Crown Ether Complexes with Supramolecular cations 91... 

In this volume we have collected 10 review chapters from distinguished scientists who have contributed extensively to the study and development of supramolecular assemblies that contain metals and metal-like elements with unusual structures and morphologies and possess potentially useful (and applicable) physical and biological properties. The first chapter by K. Ariga et al. is a general discussion of supramolecular structures that contain inorganic building blocks for hybrid lipid thin films, layer-by-layer assemblies, structure transcription, and functional mesoporous hybrids. This is followed by two chapters, the first by M. L. Kistler et al., who describe the self-assembly of hydrophilic polyoxometalate (POM) macro-anions and examine the structure and behavior of POM macro-ions in solution. This is followed by a chapter by S. K. Das, who provides an overview of the supramolecular features of POM-supported transition metal complexes, POM-crown ether complexes with supramolecular cations, and supramolecular water clusters associated with POMs. 

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