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Bi4 Te44+ -A Cube-Shaped, Polycationic Main Group Element Cluster.

Johannes Beck1, Michael Dolg2, Stefan Schlüter1

  • 1Institut für Anorganische Chemie der Universität Bonn Gerhard-Domagk-Strasse 1, 53121 Bonn (Germany) Fax: (+49) 228-735660.

Angewandte Chemie (International Ed. in English)
|May 2, 2018
PubMed
Summary

The novel cube-shaped bismuth telluride cation (Bi4Te44+) has an unusual structure due to having two more valence electrons than related clusters. This finding advances understanding of Zintl phases and cluster chemistry.

Keywords:
ab initio calculationsbismuthcluster compoundspolycationstellurium

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Area of Science:

  • Inorganic Chemistry
  • Solid-State Chemistry

Background:

  • Square-antiprismatic 38-electron clusters like Bi82+ and Sn86- are common in Zintl phases.
  • The electronic structure of clusters dictates their geometric arrangement.

Purpose of the Study:

  • To investigate the structural and electronic properties of the Bi4Te44+ cation.
  • To explain the deviation from typical cluster geometries.

Main Methods:

  • Synthesis of the chloroaluminate salt of Bi4Te44+ from acidic AlCl3/Na[AlCl4] melts.
  • Structural characterization of the resulting compound.

Main Results:

  • Discovery of a unique cube-shaped structure for the Bi4Te44+ cation.
  • The cube structure is attributed to an electron count of 40 valence electrons, two more than typical 38-electron clusters.
  • This electron count explains the deviation from the square-antiprismatic geometry.

Conclusions:

  • The Bi4Te44+ cation represents a new structural motif in Zintl cluster chemistry.
  • Electron count is a critical determinant of cluster geometry, even when exceeding typical electron counts.