The Crystal Structure of Bi8(AlCl4)2 and the Crystal Structure, Conductivity, and Theoretical Band Structure of Bi6Cl7 and Related Subvalent Bismuth Halides

Authors

  • Johannes Beck,

    Corresponding author
    1. Institut für Anorganische und Analytische Chemie der Justus-Liebig-Universität, Heinrich-Buff-Ring 58, D-35392 Gießen, Germany
    • Institut für Anorganische und Analytische Chemie der Justus-Liebig-Universität, Heinrich-Buff-Ring 58, D-35392 Gießen, Germany
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  • Claus J. Brendel,

    1. Anorganisch-Chemisches Institut der Universität Münster, Wilhelm-Klemm-Straße 8, D-48149 Münster, Germany
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  • Lars Bengtsson-Kloo,

    Corresponding author
    1. Inorganic Chemistry 1, University of Lund, P.O. Box 124, S-22100 Lund, Sweden
    • Inorganic Chemistry 1, University of Lund, P.O. Box 124, S-22100 Lund, Sweden
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  • Bernt Krebs,

    Corresponding author
    1. Anorganisch-Chemisches Institut der Universität Münster, Wilhelm-Klemm-Straße 8, D-48149 Münster, Germany
    • Anorganisch-Chemisches Institut der Universität Münster, Wilhelm-Klemm-Straße 8, D-48149 Münster, Germany
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  • Marita Mummert,

    1. Anorganisch-Chemisches Institut der Universität Münster, Wilhelm-Klemm-Straße 8, D-48149 Münster, Germany
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  • Alexander Stankowski,

    1. Institut für Anorganische und Analytische Chemie der Justus-Liebig-Universität, Heinrich-Buff-Ring 58, D-35392 Gießen, Germany
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  • Stefen Ulvenlund

    1. Dept. of Chemistry, Imperical College of Science Technology and Medicine, South Kensington, London SW7 2AY, U.K.
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Abstract

The methods of preparation for Bi8(AlCl4)2 and Bi6Cl7 have been improved and the single crystal structures for these cluster compounds re-investigated and re-interpreted. In addition, conductivity measurements and band structure calculations using the tight-binding approximation have been performed on Bi6Cl7 and related subvalent bismuth halides. – Bi8(AlCl4)2 consists of isolated AlCl4- anions and rather undistored square-antiprismatic Bi82+ clusters with an average Bi–Bi distance of 3.10 Å. Relatively short intercluster Bi–Bi contacts of 3.90 Å suggest weak bonding interactions between the Bi82+ units. In contrast, the structure determination of Bi6Cl7 implies that this structure should be regarded as being composed of discrete Bi95+ clusters and a polymeric BiIII–Cl anionic lattice including infinite, distorted α1[Bi2Cl24+] chains. According to the experimental and theoretical results, the Bi6X7 (X = Cl, Br) family of subvalent bismuth halide compounds are anisotropic semiconductors along the crystallographic c axis. The conductivity is mediated by the onedimensional α1[Bi2Cl24+] chains. These are interconnected with the Bi95+ clusters, which are acting as electron reservoirs. The related BiX (X = Br, I) family of subvalent bismuth halides are shown to be anisotropic semiconductors in the crystallographic b direction.

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