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Na9K16Tl~25: A New Phase Containing Naked Icosahedral Cluster Fragments Tl9 9−

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Abstract

The phase Na9K16Tl25.25(2) was synthesized by fusion of the elements in sealed Ta containers followed by quenching and annealing at 250°C. The structure established by single crystal X-ray diffraction means (P63/m, Z = 2, a = 19.376(3) Å, c = 11.480(2) Å) features Tl9 9− clusters. These are well separated by cations that bridge between, faces, edges, and vertices of the clusters; sodium appears to be essential in this role. This is the third compound known to contain Tl9 clusters, but here two of nine sites are partially occupied, which can be interpreted as a 70:30 mixture of Tl9 and Tl7 units in the same cavity. This Tl9 example also displays lower symmetry (C s ) but requires the same 2n skeletal electrons. EHTB electronic structure calculations indicate that the Fermi level intersects a finite densities-of-states (DOS), and only some bonds are optimized at EF, giving some insight regarding the site of Tl deficiency. Direct geometric relationships are found among Tl13, Tl9, Tl7 and Tl5 clusters through systematic removal of vertices.

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Acknowledgements

This research was supported by the Office of the Basic Energy Sciences, Materials Sciences Division, U. S. Department of Energy (DOE). The Ames Laboratory is operated for DOE by Iowa State University under Contract No. DE-AC02-07C.

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Authors and Affiliations

  1. Ames Laboratory—Department of Energy, Iowa State University, Ames, IA, 50011, USA

    Bin Li & John D. Corbett

  2. Department of Chemistry, Iowa State University, Ames, IA, 50011, USA

    Bin Li & John D. Corbett

Authors
  1. Bin Li
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  2. John D. Corbett
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Correspondence to John D. Corbett.

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Dedicated to Professor Dieter Fenske on the occasion of his 65th birthday.

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Li, B., Corbett, J.D. Na9K16Tl~25: A New Phase Containing Naked Icosahedral Cluster Fragments Tl9 9− . J Clust Sci 19, 331–340 (2008). https://doi.org/10.1007/s10876-007-0156-3

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  • DOI: https://doi.org/10.1007/s10876-007-0156-3

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