High‐Surface‐Area Mesoporous Germanium from Oxidative Polymerization of the Deltahedral [Ge<sub>9</sub>]<sup>4–</sup> Cluster: Electronic Structure Modulation with Donor and Acceptor Molecules

Armatas, Gerasimos S.; Kanatzidis, Mercouri G.

doi:10.1002/adma.200701751

Cited by 46 publications

(38 citation statements)

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“…Kleiner dimensionierte Halbleiterstrukturen sind dabei besonders gefragt, da diese die elektronischen und optischen Eigenschaften diskreter Quantenpunkte zeigen können. Die Oxidation von Zintl‐Phasen wie KSi und Mg 2 Ge führt zu Si‐Nanopartikeln336 und mesostrukturiertem Germanium 337. Eine weitere und vielleicht sogar effizientere Möglichkeit könnte hier die Verwendung von löslichen Zintl‐Ionen anstelle von unlöslichen Zintl‐Phasen bieten.…”

Section: Von Zintl‐ionen Zu Neuen Materialien – Perspektiven Für Dunclassified

“…Diese Oxidationen sollten prinzipiell unter Erhaltung des Ge 9 ‐Gerüsts ablaufen,8, 341 wovon auch bei der Bildung von mesoporösem Germanium ausgegangen wird 337. DFT‐Rechnungen haben gezeigt, dass Polymere, die durch mehrfache oxidative Kupplungsreaktionen gebildet werden, erstaunlich stabil sind.…”

Section: Von Zintl‐ionen Zu Neuen Materialien – Perspektiven Für Dunclassified

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Zintl‐Ionen, Käfigverbindungen und intermetalloide Cluster der Elemente der 14. und 15. Gruppe

et al. 2011

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Lange Zeit betrachtete man die Zintl‐Ionen der Elemente der 14. und 15. Gruppe für bemerkenswerte, in der Festkörperchemie angesiedelte Spezies, die einerseits durch ihre unerwarteten Zusammensetzungen und faszinierenden Strukturen auffielen, andererseits aber von nur eingeschränkter Bedeutung waren. Neue Aufmerksamkeit erfuhren die Zintl‐Ionen, als man feststellte, dass diese in festen Zintl‐Phasen vorgeformten Spezies aus ihrem Kristallverband extrahiert, in geeigneten Solventien gelöst und damit als Reaktanten und Bausteine in der Lösungschemie verfügbar gemacht werden können. Der steile Anstieg von Forschungsaktivitäten in diesem Gebiet führte zu einer Fülle neuer Verbindungen, beispielsweise durch Funktionalisierung dieser Zintl‐Ionen mit organischen Gruppen und metallorganischen Fragmenten, durch oxidative Kupplungsreaktionen unter Bildung von Dimeren, Oligomeren und Polymeren oder durch Einlagerung von Metallatomen, wobei endohedrale Cluster und intermetallische Verbindungen gebildet werden, von denen einige vielversprechende Perspektiven für Anwendungen in den Materialwissenschaften zeigen. Dieser Aufsatz berichtet über die enormen Fortschritte in der Chemie der Zintl‐Ionen mit Hauptaugenmerk auf deren Herstellung, Eigenschaften, Strukturen und theoretischer Beschreibung.

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Section: Von Zintl‐ionen Zu Neuen Materialien – Perspektiven Für Dunclassified

Zintl‐Ionen, Käfigverbindungen und intermetalloide Cluster der Elemente der 14. und 15. Gruppe

et al. 2011

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“…[1][2][3][4][5] Several approaches have been proposed for preparing nanoporous germanium such as electrochemical etching of Ge wafers, 6-8 chemical vapor deposition, 4,9,10 chemical reduction of porous GeO 2 , 11 liquid-crystaltemplated chemical method 3,4 and electrochemical deposition in room temperature ionic liquids. [1][2][3][4][5] Several approaches have been proposed for preparing nanoporous germanium such as electrochemical etching of Ge wafers, 6-8 chemical vapor deposition, 4,9,10 chemical reduction of porous GeO 2 , 11 liquid-crystaltemplated chemical method 3,4 and electrochemical deposition in room temperature ionic liquids.…”

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Preparation of a porous nanostructured germanium from GeO₂via a “reduction–alloying–dealloying” approach

et al. 2015

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“…The use of soluble Zintl clusters for the preparation of unique materials was pioneered by Haushalter and O'Connor in the 1980s in their work on magnetic spin glasses, electronic materials, and metallic coatings (8)(9)(10)(11)(12)(13). Since that time, scientists have pursued new materials utilizing various Zintl ion precursors to both ionically and covalently link the cluster anions into oligomers (14)(15)(16)(17)(18), polymers (19,20), network solids (21)(22)(23), and nanomaterials (24)(25)(26). Simultaneously, gas-phase chemists have prepared bare (e.g., ligand-free) clusters in molecular beams, studied their size-dependent properties, and explored possible condensed-phased manifestations (27)(28)(29)(30).…”

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Photoelectron spectroscopic and computational studies of the Pt@Pb101- and Pt@Pb121-/2- anions

Grubisic

Wang

et al. 2011

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

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A combination of anion photoelectron spectroscopy and density functional theory calculations has elucidated the geometric and electronic structure of gas-phase endohedral Pt/Pb cage cluster anions. The anions, Pt@Pb 10 1− and Pt@Pb 12 1− were prepared from "preassembled" clusters generated from crystalline samples of ½Kð2,2,2-cryptÞ 2 ½Pt@Pb 12 that were brought into the gas phase using a unique infrared desorption/photoemission anion source. The use of crystalline ½Kð2,2,2-cryptÞ 2 ½Pt@Pb 12 also provided access to K½Pt@Pb n − anions in the gas phase (i.e., the K þ salts of the Pt@Pb n 2− anions endohedral complex is the only bare cluster that has been structurally characterized in the solid state, solution, and the gas phase.endohedral clusters | negative ions | mass spectrometry T he synthesis, characterization, and solution chemistry of the soluble main group polyanions (i.e., Zintl ions) have a 120-y history (1) that has been well reviewed (2-7). The use of soluble Zintl clusters for the preparation of unique materials was pioneered by Haushalter and O'Connor in the 1980s in their work on magnetic spin glasses, electronic materials, and metallic coatings (8-13). Since that time, scientists have pursued new materials utilizing various Zintl ion precursors to both ionically and covalently link the cluster anions into oligomers (14-18), polymers (19,20), network solids (21-23), and nanomaterials (24-26). Simultaneously, gas-phase chemists have prepared bare (e.g., ligand-free) clusters in molecular beams, studied their size-dependent properties, and explored possible condensed-phased manifestations (27-30). Especially notable was the discovery of C 60 (31) in molecular beam experiments and its subsequent macroscopic synthesis (32). Several other cluster species (not yet assembled into solids) show unusual gas-phase stability (e.g., metcar cages Ti 8 C 12 and Zr 8 C 12 , refs. 33 and 34, and Al 13 1− -type cluster anions comprising icosahedral cages of group 13 elements with one atom inside; i.e., Al@Al 12 1− , refs. 27, 35, and 36). Traditional inorganic cluster compounds are stabilized by ligand spheres that reduce cluster-core interactions. By contrast, bare gas-phase clusters devoid of ligands are vulnerable to coalescence. Combining the attributes of both are salts composed of Zintl cluster anions and their countercations. Not only are Zintl cluster anions ligand free with several structural similarities to gas-phase clusters (e.g., Pt@Pb 12 2− is isostructural to Al 13 1− and the As 20 shell of As@Ni 12 @As 20 3− is isostructural to Ti 8 C 12 and C 20 ), but they can also be prepared in macroscopic quantities, fully characterized, and used in subsequent reactions. Several researchers (3,14,(37)(38)(39)(40)(41)(42)(43)(44)(45)(46)(47)(48) have prepared and isolated a number of salts of endohedral Zintl anion clusters with unprecedented structures and unique properties; e.g., σ-aromaticity, paramagnetism, and remarkable dynamic exchange processes. These "intermetalloid" clusters (3, 5, 48-51) display struct...

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High‐Surface‐Area Mesoporous Germanium from Oxidative Polymerization of the Deltahedral [Ge₉]^4– Cluster: Electronic Structure Modulation with Donor and Acceptor Molecules

Cited by 46 publications

References 24 publications

Zintl‐Ionen, Käfigverbindungen und intermetalloide Cluster der Elemente der 14. und 15. Gruppe

Zintl‐Ionen, Käfigverbindungen und intermetalloide Cluster der Elemente der 14. und 15. Gruppe

Preparation of a porous nanostructured germanium from GeO₂via a “reduction–alloying–dealloying” approach

Photoelectron spectroscopic and computational studies of the Pt@Pb101- and Pt@Pb121-/2- anions

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High‐Surface‐Area Mesoporous Germanium from Oxidative Polymerization of the Deltahedral [Ge9]4– Cluster: Electronic Structure Modulation with Donor and Acceptor Molecules

Cited by 46 publications

References 24 publications

Zintl‐Ionen, Käfigverbindungen und intermetalloide Cluster der Elemente der 14. und 15. Gruppe

Zintl‐Ionen, Käfigverbindungen und intermetalloide Cluster der Elemente der 14. und 15. Gruppe

Preparation of a porous nanostructured germanium from GeO2via a “reduction–alloying–dealloying” approach

Photoelectron spectroscopic and computational studies of the Pt@Pb101- and Pt@Pb121-/2- anions

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High‐Surface‐Area Mesoporous Germanium from Oxidative Polymerization of the Deltahedral [Ge₉]^4– Cluster: Electronic Structure Modulation with Donor and Acceptor Molecules

Preparation of a porous nanostructured germanium from GeO₂via a “reduction–alloying–dealloying” approach