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Total Structure and Optical Properties of a Phosphine/Thiolate-Protected Au24 Nanocluster

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    Total Structure and Optical Properties of a Phosphine/Thiolate-Protected Au24 Nanocluster
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    † Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States
    ‡ Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, United States
    § Department of Theoretical and Computational Molecular Science, Institute for Molecular Science, Myodaiji, Okazaki, 444-8585, Japan
    [email protected]
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    Cite this: J. Am. Chem. Soc. 2012, 134, 50, 20286–20289
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    https://doi.org/10.1021/ja3101566
    Published December 10, 2012
    Copyright © 2012 American Chemical Society
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    Abstract

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    We report the synthesis and total structure determination of a Au24 nanocluster protected by mixed ligands of phosphine and thiolate. Single crystal X-ray crystallography and electrospray ionization mass spectrometry (ESI-MS) unequivocally determined the cluster formula to be [Au24(PPh3)10(SC2H4Ph)5X2]+, where X = Cl and/or Br. The structure consists of two incomplete (i.e., one vertex missing) icosahedral Au12 units joined by five thiolate linkages. This structure shows interesting differences from the previously reported vertex-sharing biicosahedral [Au25(PPh3)10(SC2H4Ph)5X2]2+ nanocluster protected by the same type and number of phosphine and thiolate ligands. The optical absorption spectrum of Au24 nanocluster was theoretically reproduced and interpreted.

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    Details of the synthesis, X-ray crystallographic analysis, DFT calculations, and supporting Figures S1–S4. This material is available free of charge via the Internet at http://pubs.acs.org.

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    Cite this: J. Am. Chem. Soc. 2012, 134, 50, 20286–20289
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