Synthesis, Structure, and Behavior in Solution of the Dawson Thio Derivative [(P2W17O61)2(H4Mo4S4O6)]16–

Pilette, Marie-Anne; Floquet, Sébastien; Marrot, Jérôme; Cadot, Emmanuel

doi:10.1002/ejic.201100218

Cited by 7 publications

(7 citation statements)

References 43 publications

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“…One disordered linker is consistent with occupancy factors of 0.3 and 0.7 for the split Mo atoms while the other leads to equal 0.5 occupancy factors over the two Mo positions. Such local disorders are frequently observed in similar arrangements, and are explained properly by the statistical 180° reversal of the concerned {Mo 2 O 2 S 2 (OH 2 ) 2 } groups, then subsequently pointing their MoO terminal bonds (and alternately, their Mo–OH 2 groups) either inward or outward the anion . Furthermore, such positional disorders should be probably correlated with the distribution of the enclosed rubidium cations, found disordered at the centers of the four triangular basal units of the supertetrahedron (see Figure b).…”

Section: Resultsmentioning

confidence: 63%

Polyoxometalates Paneling through {Mo₂O₂S₂} Coordination: Cation-Directed Conformations and Chemistry of a Supramolecular Hexameric Scaffold

et al. 2012

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The chemical system based on the [Mo(2)O(2)S(2)(OH(2))(6)](2+) aqua cation (noted L) and the trivacant [AsW(9)O(33)](9-) polyoxometalate (noted POM) has been investigated. Depending upon the ionic strength and the nature of the alkali cations, these complementary components assemble to yield three different architectures derived as hexamer (1), tetramer (2), and dimer (3). This series of clusters displays the same stoichiometry {POM(6)L(9)}(36-), {POM(4)L(6)}(24-), and {POM(2)L(3)}(12-) for 1, 2, and 3, respectively, and their conditions of formation differ mainly by the nature and the concentration of the alkali cation (from Li to Cs). Structural characterizations of 1 reveal a large hexameric supramolecular scaffold (about 25 Å in diameter), which encloses a large internal hole (about 200 Å(3)) filled by water molecules and alkali cations (Na(+) or K(+)). The hexameric scaffold 1 exhibits a rare flexibility property evidenced in the solid state by two distinct conformations, either eclipsed (1a) or staggered-off (1b). Both conformations appear clearly separated by a large twist angle (~40°) and depend mainly on the composition of the internal hole. Structure of anion 2 shows a tetrahedral arrangement where the four POM units and the six connecting {Mo(2)O(2)S(2)} linkers are located at the corners and at the edges, respectively. The structure of anion 3 corresponds to the simplest arrangement, described as a dimeric association of two POM units linked by three {Mo(2)S(2)O(2)} pillars. Stability of the hexameric scaffold has been investigated in solution by (183)W and (39)K NMR and by UV-vis, showing that stability of 1 depends strongly on the proportion of potassium ions, which interfere through host-guest exchange. Density functional methodology (DFT) has been applied to compute the geometries and energies of dimer (3), tetramer (2) and hexamer (1) based on {AsW(9)O(33)} (POM) and {Mo(2)O(2)S(2)} (L) units. Calculations tend to show that internal cations act as "glue" to maintain the POM units connected through the conformationally inward-directed {Mo(2)O(2)S(2)} linkers.

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Section: Resultsmentioning

confidence: 63%

Polyoxometalates Paneling through {Mo₂O₂S₂} Coordination: Cation-Directed Conformations and Chemistry of a Supramolecular Hexameric Scaffold

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“…Both related effects arise from very weak coordination bonds between the two {Mo 4 S 4 (OH) 2 (OH 2 ) 3 } “handles” and the P 8 W 48 macrocycle. The weakness of POM-{Mo 2 O 2 S 2 } connections was already evidenced for dimeric assemblies [(PW 11 ) 2 (H 4 Mo 4 S 4 O 6 )] 10– and [(P 2 W 17 ) 2 (H 4 Mo 4 S 4 O 6 )] 16– , , which isomerize easily in cisoid or transoid species. In the present case, this behavior allows direct control of the coordination/decoordination processes induced by the inner countercations.…”

Section: Resultsmentioning

confidence: 93%

“…The dinuclear cation [Mo 2 O 2 S 2 (H 2 O) 6 ] 2+ exhibits coordination requirements restricted to three available sites on each molybdenum center, thus allowing one to develop predictable POM–{Mo 2 O 2 S 2 } based coordination chemistry. The oxothiocation has been proved to react with basic lacunary POMs such as PW 9 , AsW 9 , SiW 10 , PW 10 , PW 11 , P 2 W 15 , and P 2 W 17 to give species ranging from monomeric to tetramodular assembly.…”

Section: Introductionmentioning

confidence: 99%

Oxothiomolybdenum Derivatives of the Superlacunary Crown Heteropolyanion {P₈W₄₈}: Structure of [K₄{Mo₄O₄S₄(H₂O)₃(OH)₂}₂(WO₂)(P₈W₄₈O₁₈₄)]^30– and Studies in Solution

et al. 2012

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Reaction of the cyclic lacunary [H(7)P(8)W(48)O(184)](33-) anion (noted P(8)W(48)) with the [Mo(2)S(2)O(2)(H(2)O)(6)](2+) oxothiocation led to two compounds, namely, [K(4){Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(WO(2))(P(8)W(48)O(184))](30-) (denoted 1) and [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(P(8)W(48)O(184))](36-) (denoted 2), which were characterized in the solid state and solution. In the solid state, the structure of [K(4){Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(WO(2))(P(8)W(48)O(184))](30-) reveals the presence of two disordered {Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2+) "handles" connected on both sides of the P(8)W(48) ring. Such a disorder is consistent with the presence of two geometrical isomers where the relative disposition of the two {Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2+) handles are arranged in a perpendicular or parallel mode. Such an interpretation is fully supported by (31)P and (183)W NMR solution studies. The relative stability of both geometrical isomers appears to be dependent upon the nature of the internal alkali cations, i.e., Na(+) vs K(+), and increased lability of the two {Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2+) handles, compared to the oxo analogous, was clearly identified by significant broadening of the (31)P and (183)W NMR lines. Solution studies carried out by UV-vis spectroscopy showed that formation of the adduct [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(P(8)W(48)O(184))](36-) occurs in the 1.5-4.7 pH range and corresponds to a fast and quantitative condensation process. Furthermore, (31)P NMR titrations in solution reveal formation of the "monohandle" derivative [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(P(8)W(48)O(184))](38-) as an intermediate prior to formation of the "bishandle" derivatives. Furthermore, the electrochemical behavior of [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(P(8)W(48)O(184))](36-) was studied in aqueous medium and compared with the parent anion P(8)W(48).

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“…The stereospecific addition of the {Mo 2 O 2 S 2 } 2+ oxothiocation to monovacant anions, derived from Keggin or Dawson structures leads to the sandwich-like compounds 16À , respectively. 41,42 Both anions are geometrically similar, two {Mo 2 O 2 S 2 } entities are symmetrically bound to the four terminal oxygen atoms, delimiting the vacancy of each monovacant moiety (see Fig. 6).…”

Section: Isomerization Processes At the {Mo 4 S 4 O 4 } Central Corementioning

confidence: 99%

“…16À , respectively 41,42. Both anions are geometrically similar, two {Mo 2 O 2 S 2 } entities are symmetrically bound to the four terminal oxygen atoms, delimiting the vacancy of each monovacant moiety (see…”

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A building block strategy to access sulfur-functionalized polyoxometalate based systems using {Mo2S2O2} and {Mo3S4} as constitutional units, linkers or templates

et al. 2012

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The present tutorial review reports on the synthetic approaches for the formation of "polyoxothiometalate" compounds with special emphasis on the unique reactivity of the preformed sulfur-containing cationic building blocks {Mo(2)O(2)S(2)}(2+) and {Mo(3)S(4)}(4+) toward polyoxometalate building blocks. Such simple chemical systems, based on chemical and structural complementarities between ionic reactive moieties have led to the synthesis of a series of relevant clusters with unrivalled large nuclearity structural arrangements, such as loops, triangles, squares and boxes. Specific reaction parameters and considerations will be pointed out showing that a deliberate pure inorganic supramolecular chemistry based on weak interactions, flexibility and dynamic is possible with polyoxometalates.

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Synthesis, Structure, and Behavior in Solution of the Dawson Thio Derivative [(P₂W₁₇O₆₁)₂(H₄Mo₄S₄O₆)]^16–

Cited by 7 publications

References 43 publications

Polyoxometalates Paneling through {Mo₂O₂S₂} Coordination: Cation-Directed Conformations and Chemistry of a Supramolecular Hexameric Scaffold

Polyoxometalates Paneling through {Mo₂O₂S₂} Coordination: Cation-Directed Conformations and Chemistry of a Supramolecular Hexameric Scaffold

Oxothiomolybdenum Derivatives of the Superlacunary Crown Heteropolyanion {P₈W₄₈}: Structure of [K₄{Mo₄O₄S₄(H₂O)₃(OH)₂}₂(WO₂)(P₈W₄₈O₁₈₄)]^30– and Studies in Solution

A building block strategy to access sulfur-functionalized polyoxometalate based systems using {Mo2S2O2} and {Mo3S4} as constitutional units, linkers or templates

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Synthesis, Structure, and Behavior in Solution of the Dawson Thio Derivative [(P2W17O61)2(H4Mo4S4O6)]16–

Cited by 7 publications

References 43 publications

Polyoxometalates Paneling through {Mo2O2S2} Coordination: Cation-Directed Conformations and Chemistry of a Supramolecular Hexameric Scaffold

Polyoxometalates Paneling through {Mo2O2S2} Coordination: Cation-Directed Conformations and Chemistry of a Supramolecular Hexameric Scaffold

Oxothiomolybdenum Derivatives of the Superlacunary Crown Heteropolyanion {P8W48}: Structure of [K4{Mo4O4S4(H2O)3(OH)2}2(WO2)(P8W48O184)]30– and Studies in Solution

A building block strategy to access sulfur-functionalized polyoxometalate based systems using {Mo2S2O2} and {Mo3S4} as constitutional units, linkers or templates

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Synthesis, Structure, and Behavior in Solution of the Dawson Thio Derivative [(P₂W₁₇O₆₁)₂(H₄Mo₄S₄O₆)]^16–

Polyoxometalates Paneling through {Mo₂O₂S₂} Coordination: Cation-Directed Conformations and Chemistry of a Supramolecular Hexameric Scaffold

Polyoxometalates Paneling through {Mo₂O₂S₂} Coordination: Cation-Directed Conformations and Chemistry of a Supramolecular Hexameric Scaffold

Oxothiomolybdenum Derivatives of the Superlacunary Crown Heteropolyanion {P₈W₄₈}: Structure of [K₄{Mo₄O₄S₄(H₂O)₃(OH)₂}₂(WO₂)(P₈W₄₈O₁₈₄)]^30– and Studies in Solution