A 183W, 1H and 17O nuclear magnetic resonance study of aqueous isopolytungstates

Hastings, Jeremy J.; Howarth, Oliver W.

doi:10.1039/dt9920000209

Cited by 110 publications

(67 citation statements)

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“…This observation was explored further when we used bulky organocations to help isolate and connect {Mo 8 Ag 2 } building blocks into larger polymeric architectures. [25,26] The extension of this approach to isopolyoxotungstates [27,28] has also proved important in allowing us to isolate a family of {W 36 }-based host-guest complexes [29,30] (Figure 1). The {W 36 } itself is assembled from three {W 11 } y-metatungstate units [27,28] that are linked by a set of three connecting [WO 6 ] octahedra so that the overall structure can be rationalised as {W 36 } = {W 11 } 3 {W 1 } 3 ( Figure 1).…”

Section: Introductionmentioning

confidence: 99%

“…[25,26] The extension of this approach to isopolyoxotungstates [27,28] has also proved important in allowing us to isolate a family of {W 36 }-based host-guest complexes [29,30] (Figure 1). The {W 36 } itself is assembled from three {W 11 } y-metatungstate units [27,28] that are linked by a set of three connecting [WO 6 ] octahedra so that the overall structure can be rationalised as {W 36 } = {W 11 } 3 {W 1 } 3 ( Figure 1). This {W 36 } cluster represents the largest isopolyoxotungstate so far discovered and can be described as a ringshaped unit that features a metal-oxo framework, which resembles the [18]crown-6 ether.…”

Section: Introductionmentioning

confidence: 99%

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Hybrid Host–Guest Complexes: Directing the Supramolecular Structure through Secondary Host–Guest Interactions

Streb

McGlone

Brücher

et al. 2008

Chemistry A European J

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A set of four hybrid host-guest complexes based on the inorganic crown ether analogue [H12W36O120]12- ({W36}) have been isolated and characterised. The cluster anion features a central rigid binding site made up of six terminal oxygen ligands and this motif allows the selective binding of a range of alkali and alkali-earth-metal cations. Here, the binding site was utilised to functionalise the metal oxide-based cavity by complexing a range of protonated primary amines within the recognition site. As a result, a set of four hybrid organic-inorganic host-guest complexes were obtained whereby the interactions are highly directed specifically within this cavity. The guest cations in these molecular assemblies range from the aromatic 2-phenethylamine (1) and 4-phenylbutylamine (2) to the bifunctional aromatic p-xylylene diamine (3) and the aliphatic, bifunctional 1,6-diaminohexane (4). Compounds 1-4 were structurally characterised by single-crystal X-ray diffraction, elemental analysis, flame atomic absorption spectroscopy, FTIR and bond valence sum calculations. This comparative study focuses on the supramolecular effects of the amine guest cations and investigates their structure-directing effects on the framework arrangement arising by locking the protonated amines within the cavity of the {W36} cluster. It was shown that parts of the organic guest cation protrude from the central binding cavity and the nature of this protruding organic "tail" directs the solid-state arrangement of compounds 1-4. Guest cations with a hydrophobic phenyl tail result in an antiparallel assembly of {W36} complexes arranged in a series of pillared layers. As a consequence, no direct supramolecular interactions between {W36} clusters are observed. In contrast, bifunctional guest cations with a secondary amino binding site act as molecular connectors and directly link two cluster units thus locking the supramolecular assembly in a tilted arrangement. This direct linking of {W36} anions results in the formation of an infinite supramolecular scaffold.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Hybrid Host–Guest Complexes: Directing the Supramolecular Structure through Secondary Host–Guest Interactions

Streb

McGlone

Brücher

et al. 2008

Chemistry A European J

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“…None of the polyoxotungstates reported to date, [15] including the largest ones, [16] contains the corresponding important pentagonal {(W)W 5 } units. [17] Aque- species have Keggin-type structures).…”

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confidence: 99%

“…[17] Aque- species have Keggin-type structures). [15] The linkers, which are important for the syntheses of the two Keplerates mentioned above, can either be produced in situ from molybdate solutions under reducing conditions (which led to the deliberate synthesis of {Mo 132 }-type clusters) [1] or added in the form of [Mo…”

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confidence: 99%

Unprecedented and Differently Applicable Pentagonal Units in a Dynamic Library: A Keplerate of the Type {(W)W₅}₁₂{Mo₂}₃₀

et al. 2008

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Dedicated to Professor Peter Day on the occasion of his 70th birthdayIn the field of polyoxometalate chemistry, porous spherical molybdenum oxide-based clusters of the type {(Mo VI )Mo VI 5 } 12 (linker) 30 , [1] called Keplerates, [2a,b] are notable not only from an aesthetic point of view [2c] but also because they show properties of interest for different areas of science. Some of these clusters can act as artificial cells exhibiting gated pores while interacting specifically with their environments; others are of interest for several aspects of materials science. [3][4][5] In detail, of interest are a) solution properties in connection with a new type of assembly process leading to vesicles, including magnetic ones, [6a,b] b) the option to employ the characteristic interactions with amphiphiles for the generation of monolayers and Langmuir-Blodgett films [6c] as well as highly ordered honeycomb nanostructures at airwater interfaces, [6d] c) the integration into sol-gel-derived silica to obtain unprecedented hybrids, [6e] and d) the discovery of novel magnetic properties, [6f]

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“…). An additional and sharp signal appears at y120 ppm, the resonance of the a-metatungstate ion, a-H 2 W 12 O 40 6y [23]. A similar signal has been detected in solutions of tungstate and mandelic or isocitric acids and attributed to 2:2 complexes involving two oxygen bridges [17].…”

Section: Resultsmentioning

confidence: 60%

A multinuclear NMR study of the complexation of W(VI) with meso-2,3-dimercaptosuccinic acid (DMSA)

et al. 2000

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A 183W, 1H and 17O nuclear magnetic resonance study of aqueous isopolytungstates

Cited by 110 publications

References 11 publications

Hybrid Host–Guest Complexes: Directing the Supramolecular Structure through Secondary Host–Guest Interactions

Hybrid Host–Guest Complexes: Directing the Supramolecular Structure through Secondary Host–Guest Interactions

Unprecedented and Differently Applicable Pentagonal Units in a Dynamic Library: A Keplerate of the Type {(W)W₅}₁₂{Mo₂}₃₀

A multinuclear NMR study of the complexation of W(VI) with meso-2,3-dimercaptosuccinic acid (DMSA)

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A 183W, 1H and 17O nuclear magnetic resonance study of aqueous isopolytungstates

Cited by 110 publications

References 11 publications

Hybrid Host–Guest Complexes: Directing the Supramolecular Structure through Secondary Host–Guest Interactions

Hybrid Host–Guest Complexes: Directing the Supramolecular Structure through Secondary Host–Guest Interactions

Unprecedented and Differently Applicable Pentagonal Units in a Dynamic Library: A Keplerate of the Type {(W)W5}12{Mo2}30

A multinuclear NMR study of the complexation of W(VI) with meso-2,3-dimercaptosuccinic acid (DMSA)

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Unprecedented and Differently Applicable Pentagonal Units in a Dynamic Library: A Keplerate of the Type {(W)W₅}₁₂{Mo₂}₃₀