[Mo154(NO)14O420(OH)28(H2O)70](25 ± 5)−: A Water‐Soluble Big Wheel with More than 700 Atoms and a Relative Molecular Mass of About 24000

Müller, Achim; Krickemeyer, Erich; Meyer, J.; Bögge, Hartmut; Peters, Frank; Plass, Winfried; Diemann, E.; Dillinger, Stephan; Nonnenbruch, Fritz; Randerath, Markus; Menke, Carsten

doi:10.1002/anie.199521221

Cited by 375 publications

(187 citation statements)

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“…Although the family of known molecular wheels is large, many of them incorporate less than 32 metal ions. The only exceptions to this include fMn 84 g reported by Christou et al (13), and the giant fMo 154 g reported by Müller et al (10), which are built up by early transition metal ions. The similarity between the fPd 84 g and fMn 84 g wheel in terms of nuclearity is remarkable, especially given the radically different subunit composition.…”

Section: Resultsmentioning

confidence: 88%

“…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.…”

mentioning

confidence: 99%

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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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Section: Resultsmentioning

confidence: 88%

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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“…Lastly, reduced POM clusters are related to molybdenum blue species and usually their composition is largely unknown with substantial ongoing research. The POM molecules that are central to this work are mostly symmetric HPAs including polyoxomolybdates (POMs) and polyoxotunstates (POWs), which consist of molybdenum (Mo) and tungsten (W) metals, respectively, and oxygen atoms in the form of metal oxide polyhedrons [38][39][40]. In POMs, all 12 MO 6 (or WO 6 ) units conforming to so-called Keggin structures are "outer" surface moieties.…”

Section: Introductionmentioning

confidence: 99%

Functionalized Graphene–Polyoxometalate Nanodots Assembly as “Organic–Inorganic” Hybrid Supercapacitors and Insights into Electrode/Electrolyte Interfacial Processes

Gupta

Aberg

Carrizosa

2017

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Abstract:The stable high-performance electrochemical electrodes consisting of supercapacitive reduced graphene oxide (rGO) nanosheets decorated with pseudocapacitive polyoxometalates (phosphomolybdate acid-H 3 PMo 12 O 40 (POM) and phosphotungstic acid-H 3 PW 12 O 40 (POW)) nanodots/nanoclusters are hydrothermally synthesized. The interactions between rGO and POM (and POW) components create emergent "organic-inorganic" hybrids with desirable physicochemical properties (specific surface area, mechanical strength, diffusion, facile electron and ion transport) enabled by molecularly bridged (covalently and electrostatically) tailored interfaces for electrical energy storage. The synergistic hybridization between two electrochemical energy storage mechanisms, electrochemical double-layer from rGO and redox activity (faradaic) of nanoscale POM (and POW) nanodots, and the superior operating voltage due to high overpotential yielded converge yielding a significantly improved electrochemical performance. They include increase in specific capacitance from 70 F·g −1 for rGO to 350 F·g −1 for hybrid material with aqueous electrolyte (0.4 M sodium sulfate), higher current carrying capacity (>10 A·g −1 ) and excellent retention (94%) resulting higher specific energy and specific power density. We performed scanning electrochemical microscopy to gain insights into physicochemical processes and quantitatively determine associated parameters (diffusion coefficient (D) and heterogeneous electron transfer rate (k ET )) at electrode/electrolyte interface besides mapping electrochemical (re)activity and electro-active site distribution. The experimental findings are attributed to: (1) mesoporous network and topologically multiplexed conductive pathways; (2) higher density of graphene edge plane sites; and (3) localized pockets of re-hybridized orbital engineered modulated band structure provided by polyoxometalates anchored chemically on functionalized graphene nanosheets, contribute toward higher interfacial charge transfer, rapid ion conduction, enhanced storage capacity and improved electroactivity.

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“…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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[Mo₁₅₄(NO)₁₄O₄₂₀(OH)₂₈(H₂O)₇₀]^{(25 ± 5)−}: A Water‐Soluble Big Wheel with More than 700 Atoms and a Relative Molecular Mass of About 24000

Cited by 375 publications

References 4 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

Functionalized Graphene–Polyoxometalate Nanodots Assembly as “Organic–Inorganic” Hybrid Supercapacitors and Insights into Electrode/Electrolyte Interfacial Processes

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

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[Mo154(NO)14O420(OH)28(H2O)70](25 ± 5)−: A Water‐Soluble Big Wheel with More than 700 Atoms and a Relative Molecular Mass of About 24000

Cited by 375 publications

References 4 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

Functionalized Graphene–Polyoxometalate Nanodots Assembly as “Organic–Inorganic” Hybrid Supercapacitors and Insights into Electrode/Electrolyte Interfacial Processes

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

Contact Info

Product

Resources

About

[Mo₁₅₄(NO)₁₄O₄₂₀(OH)₂₈(H₂O)₇₀]^{(25 ± 5)−}: A Water‐Soluble Big Wheel with More than 700 Atoms and a Relative Molecular Mass of About 24000

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