Synthesis and characterization of an organic–inorganic hybrid compound: [WO₃ (2,2′-bipy)] (2,2′-bipy=2,2′-bipyridine)

Abstract

The hydrothermal synthesis and characterization of an organic–inorganic hybrid compound [WO₃(2,2′-bipy)] (2,2′-bipy=2,2′-bipyridine) is presented. This compound was characterized by various techniques including Raman and IR spectroscopy, XRD and thermogravimetric analysis. Structural analysis of the compound by Raman and IR data shows that it has a novel tungstate structure with 2,2′-bipy coordinated to tungsten. The X-ray powder diffraction data of the compound are indexed to a monoclinic cell with a=14.313(4), b=9.603(2), c=7.288(2) Å,β=102.07(2)°. The structure of [WO₃(2,2′-bip\y)] adopts a chain-like framework consisting of corner-shared distorted octahedra (WO₄N₂ ) with 2,2′-bipy acting as a bidentate ligand whose rings fan out from the chain. Upon heating, [WO₃(2,2′-bipy)] retains its structural integrity until 300 °C, followed by a gradual loss of 2,2′-bipy which leads to the formation of WO₃ at ca. 475°C. The thermal decomposition is observed to proceed through a transitional intermediate, [W₄O₁₂(2,2′-bipy)], the structure of which is proposed and discussed.

References

1. C. T. Kresge, M. E. Leonwicz, W. J. Roth, J. C. Vartuli and J. C. Beck, Nature, 1992, 359, 710.
2. Q. S. Huo, D. I. Margolese, U. Ciesla, P. Y. Feng, T. E. Gier, P. Sieger, R. Leon, P. M. Petroff, F. Schuth and G. D. Stucky, Nature, 1994, 368, 317.
3. A. Stein, M. Fendorf, T. P. Jarvie, K. T. Muller, A. J. Benesi and T. E. Mallouk, Chem. Mater., 1995, 7, 304.
4. G. G. Janauer, A. Dobley, J. Guo, P. Zavalij and M. S. Whittingham, Chem. Mater., 1996, 8, 2096.
5. P. J. Zapf, R. C. Haushalter and J. Zubieta, Chem. Mater., 1997, 9, 2019.
6. G. H. Huan, J. W. Johnson, A. J. Johnson and J. S. J. Merola, J. Solid State Chem., 1991, 91, 385.
7. C. Y. Duan, Y. P. Tian, Z. L. Liu, X. Z. You and X. Y. Huang, Inorg. Chem., 1995, 34, 1.
8. M. T. Pope, Heteropoly and Isopoly Oxometallates, Springer, Berlin, 1983.
9. P. K. Dutta, P. K. Gallagher and J. Twu, Chem. Mater., 1993, 5, 1739.
10. P. K. Dutta, P. K. Gallagher and J. Twu, Chem. Mater., 1992, 4, 847.
11. J. Twu, P. K. Dutta and C. T. Kresge, J. Phys. Chem., 1991, 95, 5267.
12. J. Twu and P. K. Dutta, J. Catal., 1990, 124, 503.
13. J. Twu and P. K. Dutta, Chem. Mater., 1992, 4, 398.
14. J. M. Stencel, Raman Spectroscopy For Catalysts, Van Nostrand Reinhold, New York, 1990.
15. J. Fuchs, R. Palm and H. Hartl, Angew. Chem., Int. Ed. Engl., 1996, 35, 2651.
16. W. P. Griffith and T. D. Wickins, J. Chem. Soc. A, 1966, 1087.
17. W. P. Griffith and T. D. Wickins, J. Chem. Soc. A, 1969, 1066.
18. F. D. Hardeastle and I. E. Wachs, J. Raman Spectrosc., 1995, 26, 397.
19. J. A. Horsely, I. E. Waachs, J. M. Brown, G. H. Via and F. D. Hardcastle, J. Phys. Chem., 1987, 91, 4014.
20. M. Daturi, G. Busca, M. M. Borel, A. Leclaire and P. Piaggio, J. Phys. Chem. B, 1997, 101, 4358.
21. J. Hanuza, M. Maczka and J. H. van der Maas, J. Solid State Chem., 1995, 117, 177.
22. S. A. Bagshaw and R. P. Cooney, J. Mater. Chem., 1994, 4, 557.
23. J. A. Bartlett and R. P. Cooney, Spectrochim. Acta., Part A, 1987, 43, 1543.
24. D. A. Barker, L. A. Summers and R. P. Cooney, J. Mol. Struc., 1987, 159, 249.
25. M. F. Daniel, B. Desbat, J. C. Lassegues, B. Gerand and M. Friglarz, J. Solid State Chem., 1987, 67, 235.
26. J. S. Struki and J. L. Walter, Spectrochim. Acta., Part A, 1971, 27, 223.
27. P. K. Dutta and J. A. Incavo, J. Phys. Chem., 1987, 91, 4443.
28. J. Twu, C. J. Chuang, K. I. Chang, C. H. Yang and K. H. Chen, Appl. Catal. B: Environ., 1997, 12, 309.
29. J. Twu, C. F. Shih, T. H. Guo and K. H. Chen, J. Mater. Chem., 1997, 7, 2273.
30. P. E. Werner, L. Erikson and M. Westdhal, J. Appl. Crystallogr., 1985, 18, 367.
31. G. Ramis, C. Cristina, A. S. Elmi and P. Villa, J. Mol. Catal., 1990, 61, 319.
32. N. S. P. Bhuvanesh, S. Uma, G. N. Subbanna and J. Gopalakrishnan, J. Mater. Chem., 1995, 5, 927.
33. V. H. J. Becher, Z. Anorg. Allg. Chem., 1981, 474, 63.