Synthesis and Crystal Structures of the Ligand-Stabilized Silver Chalcogenide Clusters [Ag154Se77(dppxy)18], [Ag320(StBu)60S130(dppp)12], [Ag352S128(StC5H11)96], and [Ag490S188(StC5H11)114]

Authors

  • Christopher E. Anson Dr.,

    1. Institut für Anorganische Chemie, Universität Karlsruhe, Engesserstrasse 15, 76131 Karlsruhe, Germany, Fax: (+49) 721-608-8440
    2. Institut für Nanotechnologie, Forschungszentrum Karlsruhe, Postfach 3640, 76021 Karlsruhe, Germany
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  • Andreas Eichhöfer Dr.,

    1. Institut für Anorganische Chemie, Universität Karlsruhe, Engesserstrasse 15, 76131 Karlsruhe, Germany, Fax: (+49) 721-608-8440
    2. Institut für Nanotechnologie, Forschungszentrum Karlsruhe, Postfach 3640, 76021 Karlsruhe, Germany
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  • Ibrahim Issac Dr.,

    1. Institut für Anorganische Chemie, Universität Karlsruhe, Engesserstrasse 15, 76131 Karlsruhe, Germany, Fax: (+49) 721-608-8440
    2. Institut für Nanotechnologie, Forschungszentrum Karlsruhe, Postfach 3640, 76021 Karlsruhe, Germany
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  • Dieter Fenske Prof.,

    1. Institut für Anorganische Chemie, Universität Karlsruhe, Engesserstrasse 15, 76131 Karlsruhe, Germany, Fax: (+49) 721-608-8440
    2. Institut für Nanotechnologie, Forschungszentrum Karlsruhe, Postfach 3640, 76021 Karlsruhe, Germany
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  • Olaf Fuhr Dr.,

    1. Institut für Anorganische Chemie, Universität Karlsruhe, Engesserstrasse 15, 76131 Karlsruhe, Germany, Fax: (+49) 721-608-8440
    2. Institut für Nanotechnologie, Forschungszentrum Karlsruhe, Postfach 3640, 76021 Karlsruhe, Germany
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  • Paloma Sevillano Dr.,

    1. Institut für Anorganische Chemie, Universität Karlsruhe, Engesserstrasse 15, 76131 Karlsruhe, Germany, Fax: (+49) 721-608-8440
    2. Institut für Nanotechnologie, Forschungszentrum Karlsruhe, Postfach 3640, 76021 Karlsruhe, Germany
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  • Claudia Persau Dr.,

    1. Institut für Anorganische Chemie, Universität Karlsruhe, Engesserstrasse 15, 76131 Karlsruhe, Germany, Fax: (+49) 721-608-8440
    2. Institut für Nanotechnologie, Forschungszentrum Karlsruhe, Postfach 3640, 76021 Karlsruhe, Germany
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  • Dietmar Stalke Prof. Dr.,

    1. Institut für Anorganische Chemie, Universität Göttingen, Tammannstrasse 4, 37077 Göttingen, Germany
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  • Jiatao Zhang Dr.

    1. Institut für Anorganische Chemie, Universität Karlsruhe, Engesserstrasse 15, 76131 Karlsruhe, Germany, Fax: (+49) 721-608-8440
    2. Institut für Nanotechnologie, Forschungszentrum Karlsruhe, Postfach 3640, 76021 Karlsruhe, Germany
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  • This work was supported by the DFG (Center for Functional Nanostructures) and the Fonds der Chemischen Industrie. We are grateful to Dr. H. Rösner (Institut für Nanotechnologie, Forschungszentrum Karlsruhe) for the measurement of TEM images, and to Dr. G. Buth (Institut für Synchrotronstrahung, Forschungszentrum Karlsruhe) for assistance in measuring the X-ray dataset for 4 on the SCD beamline of the ANKA synchrotron. dppxy=1,4-bis(diphenylphosphanylmethyl)benzene; dppp=1,3-bis(diphenylphosphanyl)propane.

Abstract

original image

The reaction of silver thiolates with Se(SiMe3)2 or S(SiMe3)2 in the presence of bidentate phosphanes leads to the formation of very large cluster molecules with distorted spherical metal–chalcogenide cores with diameters of 2–4 nm. The surfaces of these cores are protected by thiolate and phosphane ligands. Structural analyses show a higher degree of disorder with increasing number of Ag atoms. The compound with the highest silver content (see figure) has an idealized formulation [Ag490S188(StC5H11)114].

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