Layered ionic liquid-crystalline organisations built from nano-capsules [Mo132O312S60(SO4)x(H2O)132−2x](12 + 2x)−and DODA+cations

Floquet, Sébastien; Terazzi, Emmanuel; Korenev, Vladimir S.; Hijazi, Akram; Guénée, Laure; Cadot, Emmanuel

doi:10.1080/02678292.2014.896054

Cited by 16 publications

(26 citation statements)

References 21 publications

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“…Five IR bands at 853 (m), 792 (s), 723 (s), 628 (w) and 567 cm ‐1 occurred for [(NH 4 ) 42 [Mo VI 72 Mo V 60 O 372 (CH 3 COO) 30 (H 2 O) 72 ] structures and (NH 4 ) 2 (MimAM) 40 [Mo 132 O 372 (CH 3 COO) 30 (H 2 O) 72 ] (see Figure ). Furthermore, the band at 1403 cm −1 , attributed to NH 4 + counter‐cations, is still present in the final material indicating that not all NH 4 + have been replaced by the organic cations in agreement with previous studies . Also, the IR bands at 2930 and 2870 cm ‐1 are characteristic of alkyl chain [42b] .…”

Section: Resultssupporting

confidence: 88%

An organic‐inorganic heterogeneous catalyst based on Keplerate polyoxometalates for oxidation of dibenzothiophene derivatives with Hydrogen peroxide

Fareghi‐Alamdari

Zekri

Moghadam

et al. 2018

Applied Organom Chemis

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An organic-inorganic material (NH 4 ) 2 (MimAM) 40 [Mo 132 O 372 (CH 3 COO) 30 (H 2 O) 72 ] have been synthesized by reacting [(NH 4 ) 42 [Mo VI 72 Mo V 60 O 372 (CH 3 COO) 30 (H 2 O) 72 ] with the ionic liquid 3-Aminoethyl-1-methylimidazolium bromide. The catalyst showed remarkably a high catalytic performance in the oxidation of dibenzothiophene (DBT) derivatives with H 2 O 2 35% as a safe and green oxidant. The main parameters affecting the process including catalyst, acid additive, hydrogen peroxide amounts and temperature have been investigated in detail. Sulfur removal of DBT in n-heptane reached to 98.3% yield at 40°C using 2.5 mmol H 2 O 2 and 100 mg of (NH 4 ) 2 (MimAM) 40 [Mo 132 O 372 (CH 3 COO) 30 (H 2 O) 72 ] after 90 min. Underthe optimal conditions, BT (benzothiophene), DBT (dibenzothiophene) and 4,6-DMDBT (4,6-dimethyl-dibenzothiophene) achieved high desulfurization efficiency. Our results showed that the reactivity order of different model sulfur compounds are thiophene <4,6-dimethyl dibenzothiophene< dibenzothiophene. The catalysts could be easily separated from the reaction solution by simple filtration and recycled for several times without loss of activity.

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Section: Resultssupporting

confidence: 88%

An organic‐inorganic heterogeneous catalyst based on Keplerate polyoxometalates for oxidation of dibenzothiophene derivatives with Hydrogen peroxide

Fareghi‐Alamdari

Zekri

Moghadam

et al. 2018

Applied Organom Chemis

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“…15 Then, the full understanding of the plugging process of the 20 pores of the capsule remains an important challenge for further developments in supramolecular chemistry such as i) catalysis in confined environment 16 or at the surface of the capsule, 17 ii) ionic/molecular recognition for ion trapping, iii) the control of the spontaneous selfassembly of "blackberry" aggregates and iv) the design of Keplerate-based materials. 18 In a previous work, we reported that 1 H DOSY NMR methodology can be applied successfully to probe the interactions of the NMe 4 + cations with the {Mo 9 O 6 S 3 } pores of a sulphurated Keplerate, allowing the first quantitative analysis of this type of plugging process. 19 In this paper, we aim to extend this preliminary study to a series of small ammonium cations such as Me 4-x NH x + with x = 0-4 in the presence of the large oxo Keplerate {Mo 132 } ion used as NH 4 + , Na + or Li + salts.…”

Section: Introductionmentioning

confidence: 99%

Hydrophobic Effect as a Driving Force for Host–Guest Chemistry of a Multi-Receptor Keplerate-Type Capsule

et al. 2015

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ABSTRACT:The effectiveness of the interactions between various alkyl ammonium cations and the well-defined spherical Keplerate-type {Mo 132 } capsule has been tracked by 1 H DOSY NMR methodology which reveals a strong dependence of the selfdiffusion coefficient of the cationic guests balancing from the solvated to the plugging situations. Analysis of the data is fully consistent with a two-site exchange regime involving the 20 independent {Mo 9 O 9 } receptors of the capsule. Furthermore, quantitative analysis allowed determining the stability constants associated to the plugging process of the pores. Surprisingly, the affinity of the capsule for a series of cationic guests increases continuously with its apolar character as shown by the significant change of the stability constant from 370 to 6500 from NH 4 + and NEt 4 + , respectively. Such observations, supported by the thermodynamic parameters evidence that the major factor dictating selectivity in the trapping process is mainly the so-called "hydrophobic effect". Computational studies, using molecular dynamics simulations have been carried out in the conjunction of the experimental data. The analysis of the radial distribution functions g(r) reveals that NH 4 + and NMe 4 + ions behave differently in the vicinity of the capsule. The NH 4 + ions do not exhibit well-defined distributions in its close vicinity. In contrast, the NMe 4 + ions were identified as sharp distributions related to different scenario such as firmly trapped or as labile guest facing the {Mo 9 O 9 } pores. These conjugated experimental and theoretical insights should aid the exploitation of these giant polyoxometalates in solution for various applications.

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“…For instance, the substitution of acetate for butyrate ions confers a hydrophobic character to the cavity,10 while coordination processes involving Li + , Ca 2+ , Ln 3+ or [MoOH] + ions are mostly driven by the sulfate‐containing or sulfite‐containing Mo 132 capsule 11–16. Thus, Keplerate type‐capsules represent unique supramolecular objects offering a tunable spatially‐restricted environment and promising in many domains such as as catalysis,17 electric conductivity,18 non‐linear optics,19–20 liquid crystals,21–22 vesicles23 and “blackberry” aggregates 24. Recently, some reports demonstrate that chemical transformations can occur specifically within the cavity, then acting as a nanoreactor.…”

Section: Introductionmentioning

confidence: 99%

Tunable Keplerate Type‐Cluster “Mo₁₃₂” Cavity with Dicarboxylate Anions

Lai

Awada

Floquet

et al. 2015

Chemistry A European J

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The internal functionalization of the Keplerate-type capsule Mo132 has been carried out by ligand exchange leading to the formation of glutarate and succinate containing species isolated as ammonium or dimethylammonium salts. Solution NMR analysis is consistent with asymmetric inner dicarboxylate ions containing one carboxylato group grafted onto the inner side of the spheroidal inorganic shell while the second hangs toward the center of the cavity. Such a disposition has been confirmed by the single-crystal X-ray diffraction analysis of the glutarate containing {Mo132 } species. A detailed NMR solution study of the ligand-exchange process allowed determining the binding constant KL of acetate (AcO(-) ), succinate (HSucc(-) ) or glutarate (HGlu(-) ) ligands at the 30 inner coordinating sites, which vary such as K AcO -

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Layered ionic liquid-crystalline organisations built from nano-capsules [Mo₁₃₂O₃₁₂S₆₀(SO₄)_x(H₂O)₁₃₂₋₂_x]^{(12 + 2}^x⁾⁻and DODA⁺cations

Cited by 16 publications

References 21 publications

An organic‐inorganic heterogeneous catalyst based on Keplerate polyoxometalates for oxidation of dibenzothiophene derivatives with Hydrogen peroxide

An organic‐inorganic heterogeneous catalyst based on Keplerate polyoxometalates for oxidation of dibenzothiophene derivatives with Hydrogen peroxide

Hydrophobic Effect as a Driving Force for Host–Guest Chemistry of a Multi-Receptor Keplerate-Type Capsule

Tunable Keplerate Type‐Cluster “Mo₁₃₂” Cavity with Dicarboxylate Anions

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Layered ionic liquid-crystalline organisations built from nano-capsules [Mo132O312S60(SO4)x(H2O)132−2x](12 + 2x)−and DODA+cations

Cited by 16 publications

References 21 publications

An organic‐inorganic heterogeneous catalyst based on Keplerate polyoxometalates for oxidation of dibenzothiophene derivatives with Hydrogen peroxide

An organic‐inorganic heterogeneous catalyst based on Keplerate polyoxometalates for oxidation of dibenzothiophene derivatives with Hydrogen peroxide

Hydrophobic Effect as a Driving Force for Host–Guest Chemistry of a Multi-Receptor Keplerate-Type Capsule

Tunable Keplerate Type‐Cluster “Mo132” Cavity with Dicarboxylate Anions

Contact Info

Product

Resources

About

Layered ionic liquid-crystalline organisations built from nano-capsules [Mo₁₃₂O₃₁₂S₆₀(SO₄)_x(H₂O)₁₃₂₋₂_x]^{(12 + 2}^x⁾⁻and DODA⁺cations

Tunable Keplerate Type‐Cluster “Mo₁₃₂” Cavity with Dicarboxylate Anions