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DOI: 10.1039/A707959A (Paper) Reference Section for: J. Mater. Chem., 1998, 8, 1151-1156

Low temperature crystal and electronic band structure of the (BEDO–TTF)2Cl1.28(H3O)0.282.44H2O stable organic metal

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Rimma P. Shibaeva, Salavat S. Khasanov, Bakhyt Z. Narymbetov, Leokadiya V. Zorina, Larisa P. Rozenberg, Anatolii V. Bazhenov, Nataliya D. Kushch, Eduard B. Yagubskii, Carme Rovira and Enric Canadell

Abstract

A bis(ethylenedioxy)tetrathiafulvalene (BEDO–TTF) chloride was synthesized by a combined diffusion-electrocrystallization method using the [(C2H5)4N]2CuCl4 salt as supporting electrolyte. An X-ray analysis has been carried out at both room and low (160 K) temperatures: a=5.097(1), b=8.592(2), c=16.236(2) Å, α=98.13(1)o , V=703.8 Å3 (293 K) and a=5.069(2), b=8.435(6), c=16.137(4) Å, α=97.82(4)o , V=683.6 Å3 (160 K); space group P21 /b. This salt seems to be the same BEDO–TTF chloride previously reported by several groups although its composition was never firmly established. The crystal structure is characterized by the presence of Θ-type radical cation layers alternating along the c-direction with honeycomb-like polymeric networks including Cl– anions, H2O molecules and H3O+ , hydroxonium ions. The band structure and Fermi surface for different electron transfers at both 160 and 293 K have been calculated. The combination of these results with IR spectral data and analysis of the physical properties led to the conclusion that the real composition of this salt is (BEDO–TTF)2Cl1.28(H3O)0.28 2.44H2O.

References

  1. D. Schweitzer, S. Kahlich, I. Heinen, S. E. Lan, B. Nuber, H. J. Keller, K. Winzer and H. W. Helberg, Synth. Met., 1993, 56, 2827 CrossRef CAS.
  2. T. Mori, K. Oshima, H. Okuno, K. Kato, H. Mori and S. Tanaka, Phys. Rev. B, 1995, 51, 11110 CrossRef CAS.
  3. T. Mori, S. Ono, H. Mori and S. Tanaka, J. Phys. I Fr., 1996, 6, 1849 Search PubMed.
  4. A. V. Gudenko, V. B. Ginodman, V. E. Korotkov, A. V. Koshelap, N. D. Kushch, V. N. Laukhin, L. P. Rozenberg, A. G. Khomenko, R. P. Shibaeva and E. B. Yagubskii, in The Physics and Chemistry of Organic Superconductors, ed. G. Saito and S. Kagoshima, Springer-Verlag, Berlin, Heidelberg, 1990, p. 364 Search PubMed.
  5. M. Kurmoo, T. Mallah, P. Day, I. Marsden, M. Allan, R. H. Friend, F. L. Pratt, W. Hayes, D. Chasseau, J. Gaultier and G. Bravic, in The Physics and Chemistry of Organic Superconductors, ed. G. Saito and S. Kagoshima, Springer-Verlag, Berlin, Heidelberg, 1990, p. 290 Search PubMed.
  6. A. Kobayashi, T. Udagawa, H. Tomita, T. Naito and H. Kobayashi, Chem. Lett., 1993, 2179 CAS.
  7. I. R. Marsden, M. I. Allan, R. H. Friend, M. Kurmoo, D. Kanazawa, P. Day, G. Bravic, D. Chasseau, L. Ducasse and W. Hayes, Phys. Rev. B, 1994, 50, 2118 CrossRef CAS.
  8. N. D. Khushch, Ch. Faulmann, P. Cassoux, L. Valade, I. Malfant, J.-P. Legros, Ch. Bowlas, A. Errami and A. Kobayashi, Inorg. Chem., in press Search PubMed.
  9. E. I. Zhilyaeva, S. A. Torunova, R. N. Lyubovskaya, S. V. Konovalikhin, O. A. Dyachenko, R. B. Lyubovskii and S. I. Pesotskii, Synth. Met., 1996, 83, 7 CrossRef CAS.
  10. V. I. Andrianov, AREN-88, The System of Programs for Solving and Refinement of Crystal Structures, Institute of Crystallography AN SSSR, Moscow, 1988.
  11. G. M. Sheldrick, SHELX-93, Program for Refinement of Crystal Structures, University of Göttingen, Germany, 1993.
  12. M.-H. Whangbo and R. Hoffmann, J. Am. Chem. Soc., 1978, 100, 6093 CrossRef CAS.
  13. J. Ammeter, H.-B. Bürgi, J. Thibeault and R. Hoffmann, J. Am. Chem. Soc., 1978, 100, 3686 CrossRef CAS.
  14. S. S. Khasanov, B. Zh. Narymbetov, L. V. Zorina, L. P. Rozenberg, R. P. Shibaeva, N. D. Kushch, E. B. Yagubskii, R. Rousseau and E. Canadell, Eur. Phys. J. B., in press Search PubMed.
  15. M. A. Beno, H. H. Wang, K. D. Carlson, A. M. Kini, G. M. Frankenbach, J. R. Ferraro, N. Larson, G. D. McCabe, J. Thompson, C. Purnama, M. Vashon, J. M. Williams, D. Jung and M.-H. Whangbo, Mol. Cryst. Liq. Cryst., 1990, 181, 145 CAS.
  16. R. P. Shibaeva and V. E. Zadovnik, Kristallografiya, 1993, 38, 114 Search PubMed.
  17. M. Fettouhi, L. Ouahab, D. Serhani, J.-M. Fabre, L. Ducasse, J. Amiell, R. Canet and P. Delhaes, J. Mater. Chem., 1993, 3, 1101 RSC.
  18. H. Kobayashi, R. Kato, A. Kobayashi, I. Nishio, K. Kajita and W. Sasaki, Chem. Lett., 1986, 789 CAS.
  19. (a) M.-H. Whangbo, J. M. Williams, P. C. W. Leung, M. A. Beno, T. J. Emge and H. H. Wang, Inorg. Chem., 1985, 24, 3500 CrossRef CAS; (b) J. M. Williams, H. H. Wang, T. J. Emge, U. Geiser, M. A. Beno, P. C. W. Leung, K. D. Carlson, R. Thorn and A. J. Schulz, Prog. Inorg. Chem., 1987, 35, 51 CAS; (c) Since overlap is explicitly included in extended Hückel calculations, these nteraction energies (β) should not be confused with the conventional transfer integrals (t). Although the two quantities are obviously related and have the same physical meaning, the absolute values of β are somewhat larger than those of t.
  20. V. E. Korotkov and R. P. Shibaeva, Sov. Phys. Crystallogr., 1991, 36, 509 Search PubMed.
  21. H. Mori, I. Hirabayashi, S. Tanaka and Y. Maruyama, Bull. Chem. Soc. Jpn., 1993, 66, 2156.
  22. C. C. Ferriso and D. F. Hornig, J. Chem. Phys., 1955, 23, 1464 CAS.
  23. A. F. Wells, Structural Inorganic Chemistry, Clarendon, Oxford, 5th edn., 1984 Search PubMed.
  24. R. P. Shibaeva, R. M. Lobkovskaya, L. P. Rozenberg, L. I. Buravov, A. A. Ignatiev, N. D. Kushch, E. E. Laukhina, M. K. Makova, E. B. Yagubskii and A. V. Zvarikina, Synth. Met., 1988, A27, 189 CrossRef.
  25. R. P. Shibaeva, L. P. Rozenberg, A. F. Shestakov and T. A. Khannanova, Zh. Strukt. Khimii, 1991, 32, 98 Search PubMed.
  26. M. B. Inoue, M. A. Bruck, M. Carducci and Q. Fernando, Synth. Met, 1990, 38, 353 CAS.
  27. G. Bravic, D. Chasseau, M. Kurmoo, J. Gaultier, M. J. Rosseinsky, A. Filhol and P. Day, Synth. Met., 1991, 42, 2035 CAS.
  28. M. J. Rosseinsky, M. Kurmoo, P. Day, I. R. Marsden, R. H. Friend, D. Chasseau, J. Gaultier, G. Bravic and L. Ducasse, J. Mater. Chem., 1993, 3, 801 RSC.
  29. T. Mori and H. Inokuchi, Chem. Lett., 1987, 1657 CAS.
  30. M. J. Rosseinsky, M. Kurmoo, D. R. Talham, P. Day, D. Chasseau and D. Watkin, J. Chem. Soc., Chem. Commun., 1988, 88 RSC.
  31. F. Wudl, H. Yamochi, T. Suzuki, H. Isotalo, C. Fite, H. Kasmai, K. Liou, G. Srdanov, P. Coppens, K. Maly and A. Frost-Jensen, J. Am. Chem. Soc., 1990, 112, 2461 CrossRef CAS.
  32. V. Petricek, K. Maly, P. Coppens, X. Bu, I. Cisarova and A. Frost-Jensen, Acta Crystallogr., Sect A., 1991, 47, 210 CrossRef.
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