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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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References

  1. J. D. Corbett, in S. Kauzlarich (ed.) Chemistry, Structure and Bonding of Zintl Phases and Ions. (VCH Publishers, New York, 1996), Chap. 3

  2. J. D. Corbett (2000). Angew. Chem. Int. Ed. 39, 670

    Article  CAS  Google Scholar 

  3. C. H. E. Belin and M. Tillard-Charbonnel (1993). Prog. Solid State Chem. 22, 59

    Article  CAS  Google Scholar 

  4. R.W. Henning and J. D. Corbett (1997). Inorg. Chem. 36, 6045

    Article  CAS  Google Scholar 

  5. J. F. Smith and D. A. Hansen (1967). Acta Crystallogr. 22, 836

    Article  Google Scholar 

  6. Z.-C. Dong and J. D. Corbett (1994), J. Am. Chem. Soc. 116, 3429

    Article  CAS  Google Scholar 

  7. Z.-C. Dong and J. D. Corbett (1996). Inorg. Chem. 35, 2301

    Article  CAS  Google Scholar 

  8. S. Kaskel and J. D. Corbett (2000). Inorg. Chem. 39, 778

    Article  CAS  Google Scholar 

  9. Z.-C. Dong and J. D. Corbett (1995). J. Cluster Sci. 6, 187

    Article  CAS  Google Scholar 

  10. Z.-C. Dong and J. D. Corbett (1996). Inorg. Chem. 35, 1444

    Article  CAS  Google Scholar 

  11. Z.-C. Dong and J. D. Corbett (1995). J. Am. Chem. Soc. 117, 6447

    Article  CAS  Google Scholar 

  12. S. Kaskel and J. D. Corbett (2000). Inorg. Chem. 39, 3086

    Article  CAS  Google Scholar 

  13. H. Pauly, A. Weiss, and H. Witte (1968). Z. Metallkunde. 59, 554

    CAS  Google Scholar 

  14. E. Zintl and G. Brauer (1933). Z. Phys. Chem. 20B, 245

    CAS  Google Scholar 

  15. Z.-C. Dong and J. D. Corbett (1993). J. Am. Chem. Soc. 115, 11299

    Article  CAS  Google Scholar 

  16. Z.-C. Dong and J. D. Corbett (1996). Inorg. Chem. 35, 2301

    Article  CAS  Google Scholar 

  17. Z.-C. Dong and J. D. Corbett (1996). Angew. Chem., Int. Ed. 35, 1006

    Article  CAS  Google Scholar 

  18. D. P. Huang, Z.-C. Dong, and J. D. Corbett (1998). Inorg. Chem. 37, 5881

    Article  CAS  Google Scholar 

  19. D. P. Huang and J. D. Corbett (1999). Inorg. Chem. 38, 316

    Article  CAS  Google Scholar 

  20. SMART; Bruker AXS, Inc.; Madison, WI, (1996)

  21. R. H. Blessing (1995). Acta Crystallogr. A51, 33

    CAS  Google Scholar 

  22. SHELXTL; Bruker AXS, Inc.; Madison, WI, (2000)

  23. J. Ren, W. Liang, and M.-H. Whangbo (1998). CAESAR for Windows, Prime-Color Software, Inc.: North Carolina State University: Raleigh, NC

  24. D. B. Kang, D. Jung, and M.-H. Whangbo (1990). Inorg. Chem. 29, 257

    Article  CAS  Google Scholar 

  25. A. Vela and J.-L. Gázquez (1988). J. Phys. Chem. 92, 5688

    Article  CAS  Google Scholar 

  26. S. C. Sevov and J. D. Corbett (1992). Inorg. Chem. 31, 1895

    Article  CAS  Google Scholar 

  27. Z.-C. Dong and J. D. Corbett (1996). Inorg. Chem. 35, 3107

    Article  CAS  Google Scholar 

  28. B. Li and J. D. Corbett (2005). J. Am. Chem. Soc. 127, 926

    Article  CAS  Google Scholar 

  29. A. Hershaft and J. D. Corbett (1963). Inorg. Chem. 2, 979

    Article  CAS  Google Scholar 

  30. R. M. Friedman and J. D. Corbett (1973). Inorg. Chem. 12, 1134

    Article  CAS  Google Scholar 

Download references

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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