Syntheses and 31P NMR Studies of Cyclic Oxothiomolybdate(V) Molecular Rings: Exchange Properties and Crystal Structures of the Monophosphate Decamer [(H2PO4)Mo10S10O10(OH)11(H2O)2]2 and the Diphosphate Dodecamer [(HPO4)2Mo12S12O12(OH)12(H2O)2]4

Cadot, Emmanuel; Salignac, Bernadette; Loiseau, Thierry; Dolbecq, Anne; Sécheresse, Francis

doi:10.1002/(sici)1521-3765(19991105)5:11<3390::aid-chem3390>3.3.co;2-2

Cited by 9 publications

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“…Our group has recently developed the synthesis of a new family of cyclic oxothiomolybdates, exhibiting various nuclearities and geometries according to the nature of the encapsulated template 3. These anions crystallize as alkali salts, and the solid‐state structures of these salts are sometimes spectacular, from one‐dimensional alkali chains4 to three‐dimensional microporous materials 5. We have recently described the lithium salt of an octanuclear wheel built around a central W VI O 6 octahedron 6.…”

Section: Introductionmentioning

confidence: 99%

Octanuclear Oxothiomolybdate(V) Rings: Structure and Ionic‐Conducting Properties

Peloux

Dolbecq

Barboux

et al. 2004

Chemistry A European J

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A family of alkali salts of octanuclear oxothiomolybdate rings has been synthesized by crystallization of the [Mo(8)S(8)O(8)(OH)(8)[HMO(5)(H(2)O)]](3-) (noted HMo(8)M(3-); M=Mo, W) and [Mo(8)S(8)O(8)(OH)(8)(C(2)O(4))](2-) (noted Mo(8)ox(2-)) anions in an aqueous solution of ACl (A=Li, Na, K, Rb). Single-crystal X-ray diffraction experiments have been performed showing that the alkali salts exhibit a similar three-dimensional structure. Disordered alkali ions form columns to which the anionic rings are anchored. Ionic-conductivity measurements on pressed pellets have revealed two different behaviors. The lithium salts of HMo(8)M(3-) (M=Mo, W) are moderately good proton conductors at room temperature (sigma=10(-5) S cm(-1)) and the profile of conductivity as a function of relative humidity shows that the conductivity is due to surface-proton motion (particle-hydrate-type mechanism). On the other hand, the lithium salt of Mo(8)ox(2-) competes with the best crystalline lithium conductors at room temperature (sigma=10(-3) S cm(-1)), and (7)Li NMR experiments confirm the mobility of the lithium ions along the one-dimensional channels of this material.

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Section: Introductionmentioning

confidence: 99%

Octanuclear Oxothiomolybdate(V) Rings: Structure and Ionic‐Conducting Properties

Peloux

Dolbecq

Barboux

et al. 2004

Chemistry A European J

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“…(i) POMs as inorganic crown ethers and cryptands: POMs can offer versatile platforms for cation coordination, which are different from those of the organic counterparts, and one of the next targets would be to substitute oxygen (O 2– ) of POMs with sulfur (S 2– ), selenium (Se 2– ), etc. 75 to tune the coordination environment. (ii) POM-based ionic solids as cation-exchangers: the next target would be to explore cooperative effects of the selectively adsorbed cations and POMs,55 especially as optical materials, magnetic materials, solid catalysts, etc.…”

Section: Discussionmentioning

confidence: 99%

Frontiers and progress in cation-uptake and exchange chemistry of polyoxometalate-based compounds

Uchida

2019

Chem. Sci.

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“…A dodecanuclear ring can also be formed containing two [HPO4] 2-or two [P2O7] 4-anions [59]. An interesting deviation from the ring-shaped structural archetype was reported recently by Cadot and co-workers when they isolated two nanosized {Mo84} and Keplerate-type {Mo132} clusters, in concentrated acetate buffer (pH 3.6) solution (see Fig.…”

Section: Polyoxothiometalatesmentioning

confidence: 99%

Building Block Libraries and Structural Considerations in the Self-assembly of Polyoxometalate and Polyoxothiometalate Systems

McAllister

Miras

2017

Polyoxometalate-Based Assemblies and Functional Materials

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Inorganic metal-oxide clusters form a class of compounds that are unique in their topological and electronic versatility and are becoming increasingly more important in a variety of applications. Namely, Polyoxometalates (POMs) have shown an unmatched range of physical properties and the ability to form structures that can bridge several length scales. The formation of these molecular clusters is often ambiguous and is governed by self-assembly processes that limit our ability to rationally design such molecules. However, recent years have shown that by considering new building block principles the design and discovery of novel complex clusters is aiding our understanding of this process. Now with current progress in thiometalate chemistry, specifically polyoxothiometalates (POTM), the field of inorganic molecular clusters has further diversified allowing for the targeted development of molecules with specific functionality. This chapter discusses the main differences between POM and POTM systems and how this affects synthetic methodologies and reactivities. We will illustrate how careful structural considerations can lead to the generation of novel building blocks and further deepen our understanding of complex systems.

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Syntheses and 31P NMR Studies of Cyclic Oxothiomolybdate(V) Molecular Rings: Exchange Properties and Crystal Structures of the Monophosphate Decamer [(H2PO4)Mo10S10O10(OH)11(H2O)2]2 and the Diphosphate Dodecamer [(HPO4)2Mo12S12O12(OH)12(H2O)2]4

Cited by 9 publications

References 0 publications

Octanuclear Oxothiomolybdate(V) Rings: Structure and Ionic‐Conducting Properties

Octanuclear Oxothiomolybdate(V) Rings: Structure and Ionic‐Conducting Properties

Frontiers and progress in cation-uptake and exchange chemistry of polyoxometalate-based compounds

Building Block Libraries and Structural Considerations in the Self-assembly of Polyoxometalate and Polyoxothiometalate Systems

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