Archimedean Synthesis and Magic Numbers: “Sizing” Giant Molybdenum-Oxide-Based Molecular Spheres of the Keplerate Type

Müller, Achim; Sarkar, Sabyasachi; Shah, Syed Qaiser Nazir; Bögge, Hartmut; Schmidtmann, Marc; Sarkar, Shatarupa; Kögerler, Paul; Hauptfleisch, Björn; Trautwein, Alfred X.; Schünemann, Volker

doi:10.1002/(sici)1521-3773(19991102)38:21<3238::aid-anie3238>3.0.co;2-6

Cited by 412 publications

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“…[1,2] In particular, transition-metal-substituted polyoxometalate (TMSP) complexes are of great interest, as such mixed-metal systems can possess new or enhanced physical properties (e.g., magnetic properties). [5] Some other mag- [ netically interesting TMSP complexes are also known, such as the {Mn 19 Si 6 W 60 }, [6] {Fe 5 W 15 }, [7] {Fe 30 Mo 72 }, [8] {Ni 9 W 27 }, [9] and {Cu 14 W 36 } species. [4] More recently, a cobaltcontaining TMSP-based SMM, [{Co 4 (OH) 3 PO 4 } 4 -(PW 9 O 34 ) 4 ] 28-, was presented by Kortz.…”

Section: Introductionmentioning

confidence: 99%

Towards Nanoscopic Mn‐Containing Hybrid Polyoxomolybdates: Synthesis, Structure, Magnetic Properties, and Solution Behavior of a {Mn₆Mo₁₀} Cluster

et al. 2012

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Keywords:Polyoxometalates / Manganese / Self-assembly / Mass spectrometry / Magnetic properties A manganese-containing organic-inorganic hybrid polyoxomolybdate, (TBA) 2 [Mn II 6 Mo VI 10 (O) 12 (μ-O) 14 (μ 3 -O) 4 (tert-butyl-PO 3 ) 6 (Ac) 2 (pyridine) 4 (H 2 O) 6 ]·(CH 3 CN) 6 (1; Ac = CH 3 COO, TBA = tetrabutylammonium), was synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, and IR spectroscopy. Lindqvist hexamolybdate and manganese(III) acetylacetonate were used as starting Mo and Mn sources, respectively. Hexadecanuclear, mixed-metal 1 is characterized by a sandwich-type structural motif, whereby

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Section: Introductionmentioning

confidence: 99%

Towards Nanoscopic Mn‐Containing Hybrid Polyoxomolybdates: Synthesis, Structure, Magnetic Properties, and Solution Behavior of a {Mn₆Mo₁₀} Cluster

et al. 2012

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“…The subject of molecular magnets has greatly advanced in recent years [1][2][3][4] and has led to the synthesis of bulk samples of large paramagnetic molecules with very weak intermolecular but strong intramolecular magnetic interactions. The neutral Keplerate species, 4 ions ͑spins Sϭ5/2͒ are embedded within a molecule on the vertices of a regular Archimedean polytope, an icosidodecahedron 5 ͑see Fig.…”

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confidence: 99%

“…The neutral Keplerate species, 4 ions ͑spins Sϭ5/2͒ are embedded within a molecule on the vertices of a regular Archimedean polytope, an icosidodecahedron 5 ͑see Fig. 1͒.…”

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confidence: 99%

Exact ground state properties of the classical Heisenberg model for giant magnetic molecules

Axenovich

Luban

2001

Phys. Rev. B

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We find the exact ground state energy and magnetic moment for an arbitrary magnetic field H of the classical Heisenberg model of spins on the vertices of an icosidodecahedron. This model provides an accurate description of the magnetic properties of the giant paramagnetic molecule ͕Mo 72 Fe 30 ͖ in which 30 Fe 3ϩ ions are coupled via antiferromagnetic exchange. The strong frustration of the magnetic interaction in the molecule is relaxed when the angle between nearest-neighbor spins is 120°. We predict that the magnetic moment is linear with H until saturating at a critical field H c , and this is consistent with the results of a recent experiment at 0.46 K. We derive our results using a graph-theoretical construction and a special property, threecolorability, of the icosidodecahedron. We also consider spins on the vertices of an octahedron, icosahedron, and dodecahedron.

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“…45°, with respect to each other. Both cages in SK-1 are characterized by an endohedral arrangement of Archimedean (cuboctahedral) and Platonic (octahedral) bodies; thus we classify these molecular species as supramolecular keplerates (SK)46.…”

Section: Resultsmentioning

confidence: 99%

Ultra-large supramolecular coordination cages composed of endohedral Archimedean and Platonic bodies

et al. 2017

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Pioneered by Lehn, Cram, Peterson and Breslow, supramolecular chemistry concepts have evolved providing fundamental knowledge of the relationships between the structures and reactivities of organized molecules. A particular fascinating class of metallo-supramolecular molecules are hollow coordination cages that provide cavities of molecular dimensions promoting applications in diverse areas including catalysis, enzyme mimetics and material science. Here we report the synthesis of coordination cages with exceptional cross-sectional diameters that are composed of multiple sub-cages providing numerous distinctive binding sites through labile coordination solvent molecules. The building principles, involving Archimedean and Platonic bodies, renders these supramolecular keplerates as a class of cages whose composition and topological aspects compare to characteristics of edge-transitive {Cu2} MOFs with A3X4 stoichiometry. The nature of the cavities in these double-shell metal-organic polyhedra and their inner/outer binding sites provide perspectives for post-synthetic functionalizations, separations and catalysis. Transmission electron microscopy studies demonstrate that single molecules are experimentally accessible.

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Archimedean Synthesis and Magic Numbers: “Sizing” Giant Molybdenum-Oxide-Based Molecular Spheres of the Keplerate Type

Cited by 412 publications

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Towards Nanoscopic Mn‐Containing Hybrid Polyoxomolybdates: Synthesis, Structure, Magnetic Properties, and Solution Behavior of a {Mn₆Mo₁₀} Cluster

Towards Nanoscopic Mn‐Containing Hybrid Polyoxomolybdates: Synthesis, Structure, Magnetic Properties, and Solution Behavior of a {Mn₆Mo₁₀} Cluster

Exact ground state properties of the classical Heisenberg model for giant magnetic molecules

Ultra-large supramolecular coordination cages composed of endohedral Archimedean and Platonic bodies

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Archimedean Synthesis and Magic Numbers: “Sizing” Giant Molybdenum-Oxide-Based Molecular Spheres of the Keplerate Type

Cited by 412 publications

References 0 publications

Towards Nanoscopic Mn‐Containing Hybrid Polyoxomolybdates: Synthesis, Structure, Magnetic Properties, and Solution Behavior of a {Mn6Mo10} Cluster

Towards Nanoscopic Mn‐Containing Hybrid Polyoxomolybdates: Synthesis, Structure, Magnetic Properties, and Solution Behavior of a {Mn6Mo10} Cluster

Exact ground state properties of the classical Heisenberg model for giant magnetic molecules

Ultra-large supramolecular coordination cages composed of endohedral Archimedean and Platonic bodies

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Towards Nanoscopic Mn‐Containing Hybrid Polyoxomolybdates: Synthesis, Structure, Magnetic Properties, and Solution Behavior of a {Mn₆Mo₁₀} Cluster

Towards Nanoscopic Mn‐Containing Hybrid Polyoxomolybdates: Synthesis, Structure, Magnetic Properties, and Solution Behavior of a {Mn₆Mo₁₀} Cluster