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  • 1
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2051-2055 
    ISSN: 1434-1948
    Schlagwort(e): Gold clusters ; closo-Dodecaborate ; Conductivity ; Charging energy ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The exchange of PPh3 in Au55(PPh3)12Cl6 by Na2[B12H11SH] using a phase-transfer reaction from CH2Cl2 to water needs 6 weeks for reaction, but finally results in the quantitative formation of Au55[(B12H11SH)Na2]12Cl6 (2). Cluster 2, which is of considerable stability in aqueous solution, has been characterized by 1H-NMR, 11B-NMR, and IR spectroscopy as well as by transmission electron microscopy (TEM). The Na+ cations can be exchanged by (octyl)4N+ making the resulting cluster 4 soluble in polar organic solvents. The electrical properties of 2 and 4 are compared with those of Au55[Ph2PC6H4SO3N(octyl)4]12Cl6 (3), the ammonium derivative of the sodium salt. Cluster 3 shows the expected increase of activation energy in the temperature range of 130-250 K owing to the increase of cluster spacing compared with the sodium derivative. However, clusters 2 and 4, show electromigration in the electric field, caused by the huge amount of ionic charges in the ligand shell.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 813-817 
    ISSN: 1434-1948
    Schlagwort(e): Silsesquioxanes ; Gold clusters ; Self assembly ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A new type of gold cluster has been synthesized using the silsesquioxane derivative (cyclopentyl)7Si8O12(CH2)3SH (T8-OSS-SH) to exchange the PPh3 ligands in (PPh3)12Au55Cl6 by T8-OSS-SH quantitatively. This exchange causes several important changes in the physical and chemical behavior of the compound. Owing to the presence of cyclopentyl substituents, the cluster becomes soluble in non-polar solvents such as pentane. The stability of this compound compared with that of the PPh3-protected cluster is considerably higher meaning that decomposition in solution, and even under the high-energetic irradiation in the microscope, is not observed over longer periods of time. The increase in the total diameter from 2.1 to ca. 4.4 nm is probably responsible for these advantageous properties, supported by strong S-Au bonds. The increase in size is also expressed as an increase in the activation energy for electron-tunneling processes through the ligand shells of neighboring clusters in a densely packed pellet. This increase is from 0.16 eV for (PPh3)12Au55Cl6 to 0.26 eV for the T8-OSS-SH-protected cluster.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 3
    ISSN: 0947-6539
    Schlagwort(e): clusters ; colloids ; gold ; nanostructures ; quantum wires ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The fabrication of a supported and insulated quantum wire would be of great interest, especially if electronic information could be accessed to determine charging and conductivity profiles. The feasibility of forming one-dimensional configurations of ≈ 15 nm gold colloids and 1.4 nm gold clusters via template methods of synthesis has now been demonstrated. The template host material consisted of porous alumina membranes formed by an electrochemical anodic process. The pores of the membrane, and hence the parallel pore channels, were packed in a hexagonal array. Alumina membranes are excellent template materials because of their high degree of order, thermal and chemical stability, and optical clarity. Pore diameter was controlled by regulation of the applied anodic potential (ca. 1.4 nm V-1). The pore channels were filled by one of three methods: vacuum induction (colloids only), electrophoresis (clusters only), or immersion (clusters, which were then converted into colloids by heating). Rudimentary wires consisting of colloids and clusters were successfully formed. In both cases, the diameter of the pore channel exceeded that of the clusters or colloids. The wires thus formed conformed to the pore channel by forming helical secondary structures. It was not possible to form contiguous wires of clusters by immersion, or of colloids formed from clusters after heating. Composites (consisting of the gold-alumina system) were a bright scarlet color with an absorption maximum (λmax) at 519.5 nm. This is an unexpected result for spherical and small-diameter (10 nm) gold colloids, which normally absorb at λmax 525-530 nm, a ruby-red color. Possible causes of this small but remarkable blue shift are discussed below. A new Au55 cluster ligand system consisting of a silsesquioxane-derivatized thiol is also described.
    Zusätzliches Material: 11 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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