Synthesis, X-ray and Neutron Diffraction Characterization, and Ionic Conduction Properties of a New Oxothiomolybdate Li3[Mo8S8O8(OH)8{HWO5(H2O)}]⋅18 H2O

Dolbecq, Anne; Peloux, Charlotte du; Auberty, Anne-Laure; Mason, Sax A.; Barboux, P.; Marrot, Jérôme; Cadot, Emmanuel; Sécheresse, Francis

doi:10.1002/1521-3765(20020118)8:2<349::aid-chem349>3.0.co;2-5

Cited by 32 publications

(18 citation statements)

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“…Structure of the lithium salts of the octanuclear wheels : The HMo 9 3− and HMo 8 W 3− anions have the same overall geometry with C 4 h symmetry 6. Four {M V 2 S 2 O 2 } building blocks (M=Mo, W) are connected by hydroxo bridges and encapsulate a central M VI O 6 (M=Mo, W) octahedron.…”

Section: Resultsmentioning

confidence: 99%

“…In Li 3 [Mo 8 S 8 O 8 (OH) 8 {HWO 5 (H 2 O)}] ⋅ 18 H 2 O (noted Li 3 HMo 8 W), the anions are anchored to lacunary lithium columns. Preliminary ionic‐conductivity measurements had shown that this material is a moderately good ionic conductor ( σ =10 −5 S cm −1 at room temperature), and that the main path of conduction involves surface protons rather than lithium ions of the bulk material 6. The synthetic protocol of [Mo 8 S 8 O 8 (OH) 8 {HWO 5 (H 2 O)}] 3− has been extended to two other compounds encapsulating a central Mo VI O 6 octahedra or an oxalate (C 2 O 4 2− ) ligand, and we thus report a complete structural study of the lithium salts of the three anionic wheels and of the different alkali salts of [Mo 8 S 8 O 8 (OH) 8 (C 2 O 4 )] 2− .…”

Section: Introductionmentioning

confidence: 84%

“…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. In Li 3 [Mo 8 S 8 O 8 (OH) 8 {HWO 5 (H 2 O)}] ⋅ 18 H 2 O (noted Li 3 HMo 8 W), the anions are anchored to lacunary lithium columns.…”

Section: Introductionmentioning

confidence: 99%

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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: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 84%

Section: Introductionmentioning

confidence: 99%

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

Peloux

Dolbecq

Barboux

et al. 2004

Chemistry A European J

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“…The design and synthesis of nanoscopic inorganic clusters containing a large number of metal centers represents a fantastic challenge. Polyoxometalates (POM), often described as soluble discrete metal‐oxyde frameworks, constitute a rich family of thousands of inorganic compounds displaying various properties in catalysis,1–7 medicine,8–11 magnetism,12–17 conductivity,18, 19 or supramolecular chemistry 20–24. Especially, POM compounds exhibit unique redox properties associated with high electron storage capacities and that function as efficient electrocatalytic redox‐based reactions 25.…”

Section: Introductionmentioning

confidence: 99%

“…This fascinating class of compounds is based on the cyclization of linear [M 2 O 2 S 2 (OH) 2 ] n oligomers (M = Mo, W) around template ligands. This method has been fruitful for developing extended cyclic inorganic clusters, differing in their nuclearity and shape by the nature of the encapsulated substrate, being either mono‐ or polyphosphates,38–42 metalates,19, 43, 44 or poly‐carboxylates,45–53 such that a large variety of Mo‐rings ranging from Mo 8 to Mo 18 are now available. Particular attention was paid to solution studies using various NMR techniques and especially Diffusion Ordered Spectroscopy (DOSY)‐NMR, which was recently demonstrated to be a powerful tool for the characterization of these hollow inorganic rings 54.…”

Section: Introductionmentioning

confidence: 99%

A Decade of Oxothiomolybdenum Wheels: Synthesis, Behavior in Solution, and Electrocatalytic Properties

Lemonnier

Duval

Floquet

et al. 2011

Israel Journal of Chemistry

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The last decade has see the development of sulfur‐containing polyoxometalates (POTMs) as a subclass of the polyoxometalate family. The structural and physico‐chemical properties of this emerging class of compounds is dominating by the striking coordination properties of the [Mo2O2S2(OH2)6]2+ oxothio cation, used as a building block. The cyclic topology of this arrangement corresponds to the main feature of the {Mo2O2S2}‐based compounds, able to develop cycle‐based chemistry. The control of the linear oligomerization of the {Mo2O2S2} core is achieved by the presence of the anionic component, which acts as a template. Here, we report on recent examples which illustrate how the use of various template ions such as halide, sulfate, polyphosphate, and polycarboxylate anions allows to tune the nuclearity of the inorganic host from {Mo8} to {Mo18}. A special focus on behavior in solution is given, highlighting the dynamic and fluxional character of these host–guest systems. The Diffusion Ordered Spectroscopy (DOSY) 1H NMR, carried out on a large series of cycle‐based and capsule‐like compounds, demonstrates that such a method can be applied for the speciation of POM anions in solution. Finally, electrocatalytic behavior of the {Mo2O2S2}‐based compounds is presented. Preliminary results show that the electrocatalytic reduction of protons into hydrogen (HER) could constitute one of the most relevant applications for this class of molecular compounds.

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Self‐Assembly of Nanometer‐Scale [Cu₂₄I₁₀L₁₂]¹⁴⁺ Cages and Ball‐Shaped Keggin Clusters into a (4,12)‐Connected 3D Framework with Photoluminescent and Electrochemical Properties

et al. 2006

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The design and construction of coordination polymers from preformed metal clusters, [1] such as metal carboxylate clusters [2] and chalcogenide supertetrahedral clusters, [3] to produce new materials with unique properties have been the focus of recent research interest. However, given the importance of cuprous iodide clusters in photochemistry and photophysics, [4] as well as their considerable variety of structural forms not encountered for other iodometalates, [5] it is surprising that relatively little progress has been made in using them as building blocks for the fabrication of multidimensional coordination frameworks.[6] On the other hand, polyoxometalates (POMs), [7,8] as a unique class of metaloxide clusters, have many properties that make them attractive for applications in catalysis, biology, magnetism, optics, and medicine.[9] Impressive studies on linking of these welldefined metal-oxygen building blocks to generate giant discrete clusters and related extended structures have been performed. [10,11] However, up to now no reports have been made on the combination of these two interesting fields to prepare high-dimensional cluster-based compounds, although POM chemistry has touched an almost unprecedented number of other fields of chemistry.[9b] Such composite materials present the opportunity to generate high-dimensional nanoscopic assemblies from even larger multinanounits and also have vast potential for use in materials science by incorporation of their own physical and chemical properties.Among the many different types of POMs, we chose the Keggin heteropolyanions, as they are the most widely recognized and thoroughly studied. Furthermore, we used the N-heterocyclic ligand 4-[3-(1H-1,2,4-triazol-1-yl)propyl]-4H-1,2,4-triazole (L, see the Supporting Information) for our synthetic strategy because 1) its clawlike donor atoms and bent coordination geometry offer the possibility of incorporating more metal atoms into high-nuclearity clusters, and 2) ligands containing a large number of N atoms could partially reduce Mo VI to Mo V , [12] whereby the surface charge density of the polyanion is increased and the surface oxygen atoms are activated to facilitate formation of high-dimensional covalent networks. Herein we report the synthesis, structure, and luminescent and electrochemical properties of an unprecedented (4,12)-connected 3D network, namely, (NH 4

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Synthesis, X-ray and Neutron Diffraction Characterization, and Ionic Conduction Properties of a New Oxothiomolybdate Li3[Mo8S8O8(OH)8{HWO5(H2O)}]⋅18 H2O

Cited by 32 publications

References 36 publications

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

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

A Decade of Oxothiomolybdenum Wheels: Synthesis, Behavior in Solution, and Electrocatalytic Properties

Self‐Assembly of Nanometer‐Scale [Cu₂₄I₁₀L₁₂]¹⁴⁺ Cages and Ball‐Shaped Keggin Clusters into a (4,12)‐Connected 3D Framework with Photoluminescent and Electrochemical Properties

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Synthesis, X-ray and Neutron Diffraction Characterization, and Ionic Conduction Properties of a New Oxothiomolybdate Li3[Mo8S8O8(OH)8{HWO5(H2O)}]⋅18 H2O

Cited by 32 publications

References 36 publications

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

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

A Decade of Oxothiomolybdenum Wheels: Synthesis, Behavior in Solution, and Electrocatalytic Properties

Self‐Assembly of Nanometer‐Scale [Cu24I10L12]14+ Cages and Ball‐Shaped Keggin Clusters into a (4,12)‐Connected 3D Framework with Photoluminescent and Electrochemical Properties

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About

Self‐Assembly of Nanometer‐Scale [Cu₂₄I₁₀L₁₂]¹⁴⁺ Cages and Ball‐Shaped Keggin Clusters into a (4,12)‐Connected 3D Framework with Photoluminescent and Electrochemical Properties