Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742, USA.
Angewandte Chemie International Edition (Impact Factor: 11.26). 04/2004; 43(16):2132-4. DOI: 10.1002/anie.200353287
Source: PubMed


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    ABSTRACT: We report the experimental discovery of extremely stable metal-encapsulated superatom clusters of a group IVA element: AlPb+10 and AlPb+12. Ab initio density functional geometry optimizations at the B3LYP/LANL2DZ level result in a perfect icosahedron with an exceptionally large HOMO-LUMO gap of 3.1 eV for AlPb+12, and a related structure with D(4d) symmetry for AlPb+10, with a HOMO-LUMO gap of 2.6 eV. Their high stability is attributed to the reinforcing influence of the most favorable closed-packed structure and optimally filled electron shells.
    Full-text · Article · May 2004 · Physical Review Letters
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    ABSTRACT: Recent studies of electronic and structural properties of small doped metal clusters are reviewed. Both theoretical and experimental investigations of size and composition dependent cluster properties have emphasized the importance of the interplay between geometry and electronic structure. The conceptually simple phenomenological shell models, which have been used extensively to describe bare simple metal clusters, are extended towards different types of doped cluster species by choosing appropriate ad hoc potentials. More detailed fundamental understanding is gained by investigating the delocalized molecular orbitals as computed with ab initio density functional theory.
    No preview · Article · Jun 2004 · Current Opinion in Solid State and Materials Science
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    ABSTRACT: Bi16PdCl22 wurde in Form schwarzer, luftempfindlicher Kristalle aus den Elementen durch langsames Abkühlen einer Schmelze von 1270 K auf Raumtemperatur dargestellt. Aus Röntgenbeugungsuntersuchungen an Einkristallen geht hervor, dass die Verbindung in der triklinen Raumgruppe kristallisiert mit a = 2047, 7(4) pm, b = 2132, 1(4) pm, c = 2145, 4(4) pm und α = 91, 09(3)°, β = 95, 14(3)°, γ = 93, 16(3)°. In der Kristallstruktur finden sich Polykationen Pd@Bi104+ in Gestalt pentagonaler Archimedischer Antiprismen eingebettet in die Hohlräume eines pseudo-kubischen Raumnetzwerkes [Bi6Cl22]4- aus spitzen- und kantenverknüpften Chlorobismutat(III)-Ionen. Die 2×2×2-Überstruktur resultiert aus drei verschiedenen Hauptorientierungen der Polykationen, die im Anzahlverhältnis 3 : 3 : 2 auftreten. Die Formulierung als kationische Einschlussverbindung Pd@Bi104+ basiert auf der nur schwachen Wechselwirkung zwischen dem interstitiellen Pd0, das eine abgeschlossene Unterschale aufweist, und dem umgebenden elektronenpräzisen arachno-Cluster Bi104+.The Subchloride Bi16PdCl22: Pd@Bi104+ Polycations inside a Framework of Chloro-Bismuthate(III) AnionsBlack, air-sensitive crystals of Bi16PdCl22 were synthesized from the elements by cooling melts slowly from 1270 K to room temperature. X-ray diffraction on single-crystals revealed that the compound crystallizes with the triclinic space group and lattice parameters a = 2047.7(4) pm, b = 2132.1(4) pm, c = 2145.4(4) pm and α = 91.09(3)°, β = 95.14(3)°, γ = 93.16(3)°. In the crystal structure polycations Pd@Bi104+ with the shape of pentagonal Archimedean antiprisms (D5d symmetry) are embedded in the cavities of a pseudo-cubic framework [Bi6Cl22]4- formed by chloro-bismuthate(III) anions that share vertices and edges. The 2×2×2 super-structure results from three different main orientations of the polycations occurring with ratio 3 : 3 : 2. The weak interaction between the interstitial closed-shell Pd0 and the electron-precise arachno-cluster Bi104+ is represented by the formulation as a cationic inclusion compound Pd@Bi104+.
    No preview · Article · Nov 2004 · Zeitschrift für anorganische Chemie
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