Controlled cleavage of R₈Si₈O₁₂ frameworks: a revolutionary new method for manufacturing precursors to hybrid inorganic–organic materials

Abstract

Cube-octameric polyhedral silsesquioxanes (R₈Si₈O₁₂) react with strong acids (HX) to produce R₈Si₈O₁₁X₂ frameworks resulting from selective cleavage of one Si–O–Si linkage; subsequent hydrolysis affords R₈Si₈O₁₁(OH)₂ frameworks derived from the net hydrolysis of one Si–O–Si linkage in R₈Si₈O₁₂; these results demonstrate for the first time that readily available R₈Si₈O₁₂ frameworks can be used as precursors to incompletely condensed Si/O frameworks and have important implications for the manufacture of hybrid inorganic–organic materials based on discrete polyhedral clusters of silicon and oxygen.

References

1. (a) P. A. Agaskar, Colloids Surf., 1992, 63, 131; (b) H. C. L. Abbenhuis, H. W. G. van Herwijnen and R. A. van Santen, Chem. Commun., 1996, 1941.
2. (a) J. D. Lichtenhan, in Silsesquioxane-Based Polymers, ed. J. C. Salamone, New York, 1996; (b) J. D. Lichtenhan, Comments Inorg. Chem., 1995, 17, 115; (c) A. Tsuchida, C. Bolln, F. G. Sernetz, H. Frey and R. Mulhaupt, Macromolecules, 1997, 30, 2818; (d) A. Sellinger and R. M. Laine, Chem. Mater., 1996, 8, 1592; (e) I. Hasegawa, J. Sol-Gel Sci. Technol., 1995, 5, 93; (f) J. V. Crivello and R. Malik, J. Polym. Sci., Part A: Polym. Chem., 1997, 35, 407.
3. (a) D. Hoebbel, I. Pitsch, T. Reiher, W. Hiller, H. Jancke and D. Muller, Z. Anorg. Allg. Chem., 1989, 576, 160; (b) R. Weidner, N. Zeller, B. Deubzer and V. Frey, US Pat., 5 047 492 1991.
4. (a) M. G. Voronkov and V. Lavrent'ev, Top. Curr. Chem., 1982, 102, 199; (b) U. Dittmar, B. J. Hendan, U. Flörke and H. C. Marsmann, J. Organomet. Chem., 1995, 489, 185; (c) F. J. Feher and T. A. Budzichowski, J. Organomet. Chem., 1989, 373, 153; (d) J. F. Brown, J. Am. Chem. Soc., 1965, 87, 4317.
5. (a) A. R. Bassindale and T. E. Gentle, J. Mater. Chem., 1993, 3, 1319; (b) D. Herren, H. Bürgy and G. Calzaferri, Helv. Chim. Acta, 1991, 74, 24.
6. (a) F. J. Feher, D. A. Newman and J. F. Walzer, J. Am. Chem. Soc., 1989, 111, 1741; (b) F. J. Feher, T. A. Budzichowski, R. L. Blanski, K. J. Weller and J. W. Ziller, Organometallics, 1991, 10, 2526; (c) F. J. Feher, D. Soulivong and G. T. Lewis, J. Am. Chem. Soc., 1997, 119, 11 323; (d) F. J. Feher, S. H. Phillips and J. W. Ziller, J. Am. Chem. Soc., 1997, 119, 3397; (e) F. J. Feher and D. A. Newman, J. Am. Chem. Soc., 1990, 112, 1931.
7. R. J. P. Corriu and C. Guerin, J. Organomet. Chem., 1980, 198, 231.
8. (a) E. Rikowski and H. C. Marsmann, Polyhedron, 1997, 16, 3357; (b) J. F. Brown, L. H. Vogt and P. I. Prescott, J. Am. Chem. Soc., 1964, 86, 1120.