Formation of a Ring-Shaped Reduced “Metal Oxide” with the Simple Composition [(MoO3)176(H2O)80H32]

Müller, Achim; Krickemeyer, Erich; Bögge, Hartmut; Schmidtmann, Marc; Beugholt, Christian; Kögerler, Paul; Lu, Can‐Zhong

doi:10.1002/(sici)1521-3773(19980518)37:9<1220::aid-anie1220>3.0.co;2-g

Cited by 264 publications

(34 citation statements)

References 8 publications

(20 reference statements)

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“…In self-assembly, the observation of symmetrically favored numbers of metal nuclearity ("magic numbers") (6) or shapes with high symmetry, such as icosahedra (7) and rings (8)(9)(10), may provide a theoretical basis for the reliable and controlled fabrication of complex molecular architectures. In this respect we hypothesized that it is important to design minimal systems that use only a small number of chemical components, but with a vast library of possible architectures, and to use the techniques of structural and analytical chemistry to probe the range of accessible molecular architectures.…”

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confidence: 99%

Correlating the magic numbers of inorganic nanomolecular assemblies with a {Pd ₈₄ } molecular-ring Rosetta Stone

Miras²,

Scullion³

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

106

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Molecular self-assembly has often been suggested as the ultimate route for the bottom-up construction of building blocks atom-byatom for functional nanotechnology, yet structural design or prediction of nanomolecular assemblies is still far from reach. Whereas nature uses complex machinery such as the ribosome, chemists use painstakingly engineered step-by-step approaches to build complex molecules but the size and complexity of such molecules, not to mention the accessible yields, can be limited. Herein we present the discovery of a palladium oxometalate fPd 84 g-ring cluster 3.3 nm in diameter; ½Pd 84 O 42 ðOAcÞ 28 ðPO 4 Þ 42 70− (fPd 84 g ≡ fPd 12 g 7 ) that is formed in water just by mixing two reagents at room temperature, giving crystals of the compound in just a few days. The structure of the fPd 84 g-ring has sevenfold symmetry, comprises 196 building blocks, and we also show, using mass spectrometry, that a large library of other related nanostructures is present in solution. Finally, by analysis of the symmetry and the building block library that construct the fPd 84 g we show that the correlation of the symmetry, subunit number, and overall cluster nuclearity can be used as a "Rosetta Stone" to rationalize the "magic numbers" defining a number of other systems. This is because the discovery of fPd 84 g allows the relationship between seemingly unrelated families of molecular inorganic nanosystems to be decoded from the overall cluster magic-number nuclearity, to the symmetry and building blocks that define such structures allowing the prediction of other members of these nanocluster families.polyoxopalladates | {M84} cluster | noble metals | inorganic chemistry | self assembly F unctional nanotechnology requires control of nanomolecular architectures (1-3) that probably can only be achieved by selfassembly from the bottom up (4, 5) but this process itself is very difficult to predict, rationalize, or control. In self-assembly, the observation of symmetrically favored numbers of metal nuclearity ("magic numbers") (6) or shapes with high symmetry, such as icosahedra (7) and rings (8-10), may provide a theoretical basis for the reliable and controlled fabrication of complex molecular architectures. In this respect we hypothesized that it is important to design minimal systems that use only a small number of chemical components, but with a vast library of possible architectures, and to use the techniques of structural and analytical chemistry to probe the range of accessible molecular architectures. By conducting such solution studies, combined with structural analysis, our aim has been to understand the overall cluster nuclearity and structure to reveal the underlying principles that link symmetry to structure with the overall grand aim of the a priori design of molecular nanosystems from the bottom up using self-assembly.Here, we present the discovery of a complex self-assembled system in which the architectural beauty and molecular complexity are orchestrated by symmetry and a library of dynamic subuni...

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mentioning

confidence: 99%

Correlating the magic numbers of inorganic nanomolecular assemblies with a {Pd ₈₄ } molecular-ring Rosetta Stone

Miras²,

Scullion³

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

106

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“…POM clusters can be classified in three general categories [23][24][25]; (1) heteropolyanions are the most explored category, and they consist of metal-oxide clusters of Mo, W, V, which contain XO 4 n− type heteroanions, where X = B, Si, Ge, P, and S. Heteroanions induce stability to the clusters as well as to their lacunary derivatives generated by the removal of one or more addenda atoms. In the first category for example, belong the two well-known POM archetypes, Keggin [28], and the {Mo 132 } Keplerate cluster [29], which are all constructed using the same structural building block, {MoMo 5 }. The central building block is occupied by a pentagonal bipyramidal {MoO 7 } unit, which is surrounded by five edge-shared {MoO 6 } octahedra along the equator of the bipyramid.…”

Section: Pom-based Clusters and Supramolecular Aggregatesmentioning

confidence: 99%

“…They connect to the {Mo 8 and Browns. The most well-known Molybdenum Blue structures are the giant wheels, {Mo154} [27] and {Mo176} [28], and the {Mo132} Keplerate cluster [29], which are all constructed using the same structural building block, {MoMo5}. The central building block is occupied by a pentagonal bipyramidal {MoO7} unit, which is surrounded by five edge-shared {MoO6} octahedra along the equator of the bipyramid.…”

Section: Pom-based Clusters and Supramolecular Aggregatesmentioning

confidence: 99%

Self-Assembly in Polyoxometalate and Metal Coordination-Based Systems: Synthetic Approaches and Developments

et al. 2018

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Abstract:Utilizing new experimental approaches and gradual understanding of the underlying chemical processes has led to advances in the self-assembly of inorganic and metal-organic compounds at a very fast pace over the last decades. Exploitation of unveiled information originating from initial experimental observations has sparked the development of new families of compounds with unique structural characteristics and functionalities. The main source of inspiration for numerous research groups originated from the implementation of the design element along with the discovery of new chemical components which can self-assemble into complex structures with wide range of sizes, topologies and functionalities. Not only do self-assembled inorganic and metal-organic chemical systems belong to families of compounds with configurable structures, but also have a vast array of physical properties which reflect the chemical information stored in the various "modular" molecular subunits. The purpose of this short review article is not the exhaustive discussion of the broad field of inorganic and metal-organic chemical systems, but the discussion of some representative examples from each category which demonstrate the implementation of new synthetic approaches and design principles.

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“…6,25–31 Yongge Wei et. al , 32,33 A. Müller et al 34–47 and others 48–51 have synthesised and structurally described a huge number of nanoscale large clusters of polyoxometalates and related assemblies such as chain-like Mo 38 , ball-like Mo 132 and tyre-like Mo 176 self-assembled from Mo 36 . These enormous clusters with strong nuclearity have proved to be ideal models for nanochemistry, materials science and mesoscopic physics.…”

Section: Introductionmentioning

confidence: 99%

Insights into organic–inorganic hybrid molecular materials: organoimido functionalized polyoxomolybdates

2022

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Formation of a Ring-Shaped Reduced “Metal Oxide” with the Simple Composition [(MoO3)176(H2O)80H32]

Cited by 264 publications

References 8 publications

Correlating the magic numbers of inorganic nanomolecular assemblies with a {Pd ₈₄ } molecular-ring Rosetta Stone

Correlating the magic numbers of inorganic nanomolecular assemblies with a {Pd ₈₄ } molecular-ring Rosetta Stone

Self-Assembly in Polyoxometalate and Metal Coordination-Based Systems: Synthetic Approaches and Developments

Insights into organic–inorganic hybrid molecular materials: organoimido functionalized polyoxomolybdates

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Formation of a Ring-Shaped Reduced “Metal Oxide” with the Simple Composition [(MoO3)176(H2O)80H32]

Cited by 264 publications

References 8 publications

Correlating the magic numbers of inorganic nanomolecular assemblies with a {Pd 84 } molecular-ring Rosetta Stone

Correlating the magic numbers of inorganic nanomolecular assemblies with a {Pd 84 } molecular-ring Rosetta Stone

Self-Assembly in Polyoxometalate and Metal Coordination-Based Systems: Synthetic Approaches and Developments

Insights into organic–inorganic hybrid molecular materials: organoimido functionalized polyoxomolybdates

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Correlating the magic numbers of inorganic nanomolecular assemblies with a {Pd ₈₄ } molecular-ring Rosetta Stone

Correlating the magic numbers of inorganic nanomolecular assemblies with a {Pd ₈₄ } molecular-ring Rosetta Stone