Porous Capsules {(M)M5}12FeIII30 (M=MoVI, WVI): Sphere Surface Supramolecular Chemistry with 20 Ammonium Ions, Related Solution Properties, and Tuning of Magnetic Exchange Interactions

Todea, Ana Maria; Merca, Alice; Bögge, Hartmut; Glaser, Thorsten; Pigga, Joseph M.; Langston, Melissa L. K.; Liu, Tianbo; Prozorov, Ruslan; Luban, Marshall; Schröder, Christian; Casey, William H.; Müller, Achim

doi:10.1002/anie.200905460

Cited by 83 publications

(47 citation statements)

References 52 publications

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“…Most importantly, the construction automatically results in porosity: the mentioned capsule type has 20 flexible {Mo 9 O 9 } pores (diameter ca. 0.35 nm; see below), each of which (Figure 1 b) acts like a [27]crown‐9 polyether45 (the pores of the above mentioned smaller Keplerates are comparable to the [18]crown‐6 ethers43e). Whereas the porosity in solids, including metal–organic frameworks (MOFs), is well documented,46 less is known about the porosity of discrete molecular species despite ongoing interest in metal–organic polyhedra (MOPs; see e.g., reference 9) or in porous organic molecules (see e.g., reference 47).…”

Section: Unique Structural Features and Deliberate Synthesis Based Onmentioning

confidence: 99%

Capsules with Highly Active Pores and Interiors: Versatile Platforms at the Nanoscale

Müller

Gouzerh

2014

Chemistry A European J

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Spherical porous capsules offer new exciting approaches in chemistry, materials sciences, and in context of physical and biological phenomena. The underlying concepts are reported with particular emphasis on metal oxide based capsules of the {M132 } Keplerate type which display-due to their exceptional structural features and easy variation/derivatization as well as exchange of building units-an unmatched range of properties and offer unique opportunities for investigating a variety of basic aspects of nanoscience, including the discovery of some new phenomena, especially those related to hydrophobicity issues that are of significance for everyday life. This relies in particular on the existence of a large number of flexible crown ether type pores/channels and the possibility of changing the interior from completely hydrophilic to completely hydrophobic due to the presence of numerous easily exchangeable internal ligands/functionalities; the capsules can even be constructed so that they enclose a large number of highly active Lewis and Brønsted acid sites. The manifold of possible applications/uses are outlined as subtitles with reference to results as well as possible future studies. There are, among many others, options to control passing cations under different internal frames allowing also their separations, to conduct studies about hydrophobic recognitions and clustering of biological interest in water, controlled internal ion transport, nanoscale dewetting, and to carry out basic as well as new types of reactions under confined conditions.

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Section: Unique Structural Features and Deliberate Synthesis Based Onmentioning

confidence: 99%

Capsules with Highly Active Pores and Interiors: Versatile Platforms at the Nanoscale

Müller

Gouzerh

2014

Chemistry A European J

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“…Müller et al. reported 30 Fe III centers in Mo‐ and W‐based porous nanocapsules and a {Mo 72 Fe 30 } ball ,. Gouzerh et al.…”

Section: Introductionmentioning

confidence: 99%

Unprecedented {Fe₁₄}/{Fe₁₀} Polyoxotungstate‐Based Nanoclusters with Efficient Photocatalytic H₂ Evolution Activity: Synthesis, Structure, Magnetism, and Electrochemistry

Singh

Chen

et al. 2016

Chemistry A European J

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Novel Fe10 and Fe14 clusters [Rb9 Cs4 H37 Fe10 O34 (A-α-PW9 O31 )3 (OH)3 ]⋅36 H2 O (1) and [H3 Rb3 Fe14 (OH)12 (PO4 )6 (B-α-PW9 O34 )2 ]⋅21 H2 O (2) were synthesized and characterized in the solid state by single-crystal X-ray diffraction, IR spectroscopy, thermogravimetric analysis (TGA), and magnetic studies, and in solution by electrochemistry. Cluster 1 is a decameric Fe(III) polyanionic cluster encapsulating a cesium atom in the center. Cluster 2 is a unique tetradecanuclear Fe(III) sandwich structure with phosphate-linked units featuring two quasicubic Fe4 O4 moieties. Apparently, 2 has the highest nuclearity of all known Fe(III) sandwich-type polyoxometalate clusters. Clusters 1 and 2 also act as photocatalysts with platinum as cocatalyst for H2 evolution from light-driven water splitting. Changes in the cyclovoltammetric patterns with variations in pH were observed for 1 and 2, most likely due to intermolecular interactions among the high-nuclearity Fe(III) cluster cores and subsequent changes in the acid-base properties of the two reduced POMs. Magnetic studies provide evidence of antiferromagnetic interactions in 1 and 2. TGA showed that complexes 1 and 2 decompose between 580 and 590 °C.

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“…Furthermore, these characteristics make them economical and environmentally attractive in both academic and industrial applications [15]. Muller pointed out that giant polyoxomolybdates, porous spherical molybdenum oxide-based clusters of the type {(Mo VI ) Mo 5 VI } 12 (linker) 30 called Keplerates, show signs of interest for different areas of science [19][20][21]. However, their catalytic properties in the oxidation of organic reactions really fall behind [22,23].…”

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“…In order to study the stability of the W 72 Fe 30 at the end of the reaction, the solids recovered after the evaporation of the solvent and catalysts, were washed and analyzed by IR spectroscopy. This study was carried out for the oxidation of thioanisole catalysed by W 72 Fe 30 . The infrared spectra of the catalyst acquired at the end of the reaction in a different cycle represented no significant change in the IR spectrum at different runs (Fig.…”

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Highly Selective Oxidation of Sulfides to Sulfones by H2O2 Catalyzed by Porous Capsules

et al. 2015

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In this study, selective oxidation of different sulfides to the corresponding sulfone with hydrogen peroxide in the presence of W 72 Fe 30 is reported. W 72 Fe 30 is as an efficient catalyst for the selective oxidation of sulfides to sulfones, in high to excellent yields using 30 % hydrogen peroxide as an oxidant under optimum reaction conditions. Various sulfides containing functional groups such as double bond and hydroxyl group are successfully and selectively oxidized without affecting sensitive functionalities. Graphical Abstract Oxidation of sulfides to corresponding sulfone by H 2 O 2 in the presence of W 72 Fe 30

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Porous Capsules {(M)M₅}₁₂Fe^III₃₀ (M=Mo^VI, W^VI): Sphere Surface Supramolecular Chemistry with 20 Ammonium Ions, Related Solution Properties, and Tuning of Magnetic Exchange Interactions

Cited by 83 publications

References 52 publications

Capsules with Highly Active Pores and Interiors: Versatile Platforms at the Nanoscale

Capsules with Highly Active Pores and Interiors: Versatile Platforms at the Nanoscale

Unprecedented {Fe₁₄}/{Fe₁₀} Polyoxotungstate‐Based Nanoclusters with Efficient Photocatalytic H₂ Evolution Activity: Synthesis, Structure, Magnetism, and Electrochemistry

Highly Selective Oxidation of Sulfides to Sulfones by H2O2 Catalyzed by Porous Capsules

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Porous Capsules {(M)M5}12FeIII30 (M=MoVI, WVI): Sphere Surface Supramolecular Chemistry with 20 Ammonium Ions, Related Solution Properties, and Tuning of Magnetic Exchange Interactions

Cited by 83 publications

References 52 publications

Capsules with Highly Active Pores and Interiors: Versatile Platforms at the Nanoscale

Capsules with Highly Active Pores and Interiors: Versatile Platforms at the Nanoscale

Unprecedented {Fe14}/{Fe10} Polyoxotungstate‐Based Nanoclusters with Efficient Photocatalytic H2 Evolution Activity: Synthesis, Structure, Magnetism, and Electrochemistry

Highly Selective Oxidation of Sulfides to Sulfones by H2O2 Catalyzed by Porous Capsules

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Porous Capsules {(M)M₅}₁₂Fe^III₃₀ (M=Mo^VI, W^VI): Sphere Surface Supramolecular Chemistry with 20 Ammonium Ions, Related Solution Properties, and Tuning of Magnetic Exchange Interactions

Unprecedented {Fe₁₄}/{Fe₁₀} Polyoxotungstate‐Based Nanoclusters with Efficient Photocatalytic H₂ Evolution Activity: Synthesis, Structure, Magnetism, and Electrochemistry