Polyoxothiomolybdenum Wheels as Anionic Receptors for Recognition of Sulfate and Sulfonate Anions

Lemonnier, Jean‐François; Floquet, Sébastien; Marrot, Jérôme; Cadot, Emmanuel

doi:10.1002/ejic.200900613

Cited by 15 publications

(14 citation statements)

References 30 publications

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“…They present applications in catalysis, optics, magnetism, medicine and electrochemistry, among others. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] A recently investigated family of POMs is the polyoxovanadoborate (BVO), 21 which presents different vanadium/ boron stoichiometries and different mixed valence V IV /V V ratios. Several frameworks have been reported in the literature with different V/B stoichiometries and in which ethylenediamine and 1,3-diaminopropane, with different degrees of protonation, are present in the crystalline lattice.…”

Section: Introductionmentioning

confidence: 99%

Crystal lattice effect on the quenching of the intracluster magnetic interaction in [V₁₂B₁₈O₆₀H₆]¹⁰⁻polyoxometalate

et al. 2014

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In the present work, the synthesis and structural characterization of four new polyoxovanadoborate (BVO) frameworks based on the [V12B18O60H6](10-) polyanion are reported: (NH4)8(1,3-diapH2)[V12B18O60H6]·5H2O (1), K8(NH4)2[V12B18O60H6]·18H2O (2), K10[V12B18O60H6]·10H2O (3) and K8Cs2[V12B18O60H6]·10H2O (4). A global antiferromagnetic behaviour is observed for these 10V(IV)/2V(V) mixed valence clusters. The magnetic data of 1, 2 and 3, which present different countercation environments, show that 1 is more coupled than 2 and 3. DFT calculations show that the positive charges strongly influence the polarization mechanism of the spin density of the vanadyl groups and the extent of the magnetic orbitals, therefore corroborating the experimental observation of the quenching effect of the magnetic coupling between vanadium centres of 2 and 3.

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Section: Introductionmentioning

confidence: 99%

Crystal lattice effect on the quenching of the intracluster magnetic interaction in [V₁₂B₁₈O₆₀H₆]¹⁰⁻polyoxometalate

et al. 2014

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“…In fact, the important and in some cases dominant role of hydrogen bonding in the stabilization of host-guest inclusion complexes of ground state guests has been well established and demonstrated in the literature, for a wide range of hosts including cyclodextrins, [23][24][25][26][27][28][29] calixarenes, 30 cucurbiturils, 31,32 and other hosts. [33][34][35] Ross and Rekharsky investigated the quantitative thermodynamic contributions of hydrogen bonding in some specific cyclodextrin inclusion complexes, and reported that a single host-guest hydrogen bond contributes ca. 600 cal mol À1 to the stability (in terms of Gibbs energy) of these complexes.…”

Section: Introductionmentioning

confidence: 99%

Hydrogen bonding of excited states in supramolecular host–guest inclusion complexes

Wagner

2012

Phys. Chem. Chem. Phys.

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Host-guest inclusion complexes represent an important type of supramolecular structure, one which finds widespread applications in diverse areas including separations science, the food industry, molecular sensors and optical devices. There are several driving forces for the formation of such inclusion complexes in solution; one of the most important is hydrogen bonding between the guest and host molecules. The nature or strength of the hydrogen bonding may change upon electronic excitation of the guest, for example during fluorescence studies or when the inclusion complex is used as an optical sensor. In this Perspective article, the impact of hydrogen bonding between excited state guests and their hosts is examined in detail, in terms of the impact on the formation and stability of such excited state complexes, the effects on guest fluorescence, changes in the stability of ground state guest complexes upon electronic excitation, the application of inclusion complexes as fluorescent sensors and materials, and the use of fluorescence spectroscopy for their study.

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“…Finally, the propensity of the neutral [Mo 10 O 10 S 10 (OH) 10 (H 2 O) 5 ] complex to react with the sulfonate anion prompted us to study the reaction of this compound with a DOWEX anionic resin for which the anchoring sites are paratoluenylsulfonates. This study demonstrates that it is possible to partially graft such Mo‐rings onto the surface of a DOWEX resin, which offers a simple way to immobilize these molecular systems on surfaces 57…”

Section: Ring Design Through Template Effectmentioning

confidence: 89%

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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Polyoxothiomolybdenum Wheels as Anionic Receptors for Recognition of Sulfate and Sulfonate Anions

Cited by 15 publications

References 30 publications

Crystal lattice effect on the quenching of the intracluster magnetic interaction in [V₁₂B₁₈O₆₀H₆]¹⁰⁻polyoxometalate

Crystal lattice effect on the quenching of the intracluster magnetic interaction in [V₁₂B₁₈O₆₀H₆]¹⁰⁻polyoxometalate

Hydrogen bonding of excited states in supramolecular host–guest inclusion complexes

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

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Polyoxothiomolybdenum Wheels as Anionic Receptors for Recognition of Sulfate and Sulfonate Anions

Cited by 15 publications

References 30 publications

Crystal lattice effect on the quenching of the intracluster magnetic interaction in [V12B18O60H6]10−polyoxometalate

Crystal lattice effect on the quenching of the intracluster magnetic interaction in [V12B18O60H6]10−polyoxometalate

Hydrogen bonding of excited states in supramolecular host–guest inclusion complexes

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

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Product

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Crystal lattice effect on the quenching of the intracluster magnetic interaction in [V₁₂B₁₈O₆₀H₆]¹⁰⁻polyoxometalate

Crystal lattice effect on the quenching of the intracluster magnetic interaction in [V₁₂B₁₈O₆₀H₆]¹⁰⁻polyoxometalate