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Syntheses and Crystal Structures of the Ag[BOND]S Cluster Compounds [Ag70S20(SPh)28(dppm)10] (CF3CO2)2 and [Ag262S100(StBu)62(dppb)6]

Authors

  • Dieter Fenske Prof. Dr.,

    1. Institut für Anorganische Chemie, Universität Karlsruhe, Engesserstrasse, Geb. 30.45, 76128 Karlsruhe, Germany, Fax: (+49) 721-608-2086
    2. Institut für Nanotechnologie, Forschungszentrum Karlsruhe GmbH, Postfach 3640, 76021 Karlsruhe, Germany
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  • Claudia Persau Dr.,

    1. Institut für Anorganische Chemie, Universität Karlsruhe, Engesserstrasse, Geb. 30.45, 76128 Karlsruhe, Germany, Fax: (+49) 721-608-2086
    2. Institut für Nanotechnologie, Forschungszentrum Karlsruhe GmbH, Postfach 3640, 76021 Karlsruhe, Germany
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  • Stefanie Dehnen Dr.,

    1. Institut für Anorganische Chemie, Universität Karlsruhe, Engesserstrasse, Geb. 30.45, 76128 Karlsruhe, Germany, Fax: (+49) 721-608-2086
    2. Institut für Nanotechnologie, Forschungszentrum Karlsruhe GmbH, Postfach 3640, 76021 Karlsruhe, Germany
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  • Christopher E. Anson Dr.

    1. Institut für Anorganische Chemie, Universität Karlsruhe, Engesserstrasse, Geb. 30.45, 76128 Karlsruhe, Germany, Fax: (+49) 721-608-2086
    2. Institut für Nanotechnologie, Forschungszentrum Karlsruhe GmbH, Postfach 3640, 76021 Karlsruhe, Germany
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  • This work has been supported by the Deutsche Forschungsgemeinschaft (Center for Functional Nanostructures) and the Fonds der Chemischen Industrie. D.F. acknowledges an OVS fellowship provided by St. John's College, Cambridge; (dppm: bis(diphenylphosphanyl)methane, dppb: bis(diphenylphosphanyl)butane).

Abstract

original image

With a maximum diameter of 3.7 nm, [Ag262S100(StBu)62(dppb)6] (dppb=1,4-bis(diphenylphosphanyl)butane) is the largest structurally characterized metal chalcogenide cluster (see picture, P green, S yellow and red, Ag blue). The Ag[BOND]S substructure has a relationship to structural characteristics observed in binary Ag2S phases: tetrahedral AgS4 and AgS3P units are linked by trigonal planar AgS3 and approximately linear AgS2 units. While the cluster periphery is well ordered, the Ag and S atomic sites in the center of the cluster are disordered. This observation is in accordance with macroscopic properties of Ag2S.

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