A Molecular Composite Constructed in Aqueous Alkaline Solution from a Double Six-Ring Silicate and α-Cyclodextrin

Angewandte Chemie (International Edition in English)

Volumn 36, Issue 7, 1997, Pages 743-745

  Benner, Klaus ^a   Klüfers, Peter ^a   Schuhmacher, Jörg ^a  

^a UNIVERSITY OF KARLSRUHE   (Germany)

Author keywords

Biomineralization; Cyclodextrins; Silicon; Supramolecular chemistry

Indexed keywords

EID: 0030753846     PISSN: 05700833     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.199707431     Document Type: Article

References (21)

1. A. Dyer in Encyclopedia of Inorganic Chemistry, Vol. 8 (Ed.: R. B. King), Wiley, Chichester, 1994, p. 4364-4391; the basic idea is modified by recent authors, who discuss a common network of silicate, water, and cations [9].
2. a) S. Mann, C. C. Perry Ciba Found. Symp. 1986, 121 40-58;
3. b) A. G. Sangster, M. J. Hudson, ibid, 1986. 121, 90-107;
4. c) C. C. Perry in Biomineralization, Chemical and Biochemical Perspectives (Ed.: S. Mann, J. Webb, R. J. P. Williams), VCH, Weinheim, 1989, p. 223-256.
5. R. B. Frankel in Encyclopedia of Inorganic Chemistry, Vol. 1 (Ed.: R. B. King), Wiley, New York, 1994, p. 269-279.
6. L. Addadi, S. Weiner in Biomineralization, Chemical and Biochemical Perspectives (Ed.: S. Mann, J. Webb, R. J. P. Williams), VCH, Weinheim, 1989, p. 133-156.
7. -3 next to a potassium atom. Water content according to structural analysis: 16.7%. Further programs used: PLATON, SCHAKAL. Further details of the crystal structure investigation may be obtained from the Fachinformationszentrum Karlsruhe, D-76344 Eggenstein-Leopoldshafen (Germany), on quoting the depository number CSD-405903.
8. F. Liebau, Structural Chemistry of Silicates, Springer, Berlin, 1985, p. 97-99 and p. 194.
9. K. B. Lipkowitz, J. Org. Chem. 1991, 56, 6357-6367.
10. - bonds, which results from a geometric peculiarity of a cyclodextrin cone. It may be shown by simple geometric considerations that the distance of the O3 atoms to the center of the cone (and hence to the silicate double ring, which has a smaller diameter than the cyclodextrin) is shorter than in the case of O2 [13a]. In 1, there is only a slight correction in terms of a rotation of the silicate prism towards the O2 atoms.
11. R. K. Harris, D. Yu. Naumov, A. Samadi-Maybodi, J. Chem. Soc. Dalton Trans. 1996, 3349-3355, and the references therein.
12. D. Hoebbel, A. Vargha, B. Fahlke, G. Engelhardt, Z. Anorg. Allg. Chem. 1985, 521, 61-68.
13. It appears the potassium ions bind to the finished assembly and do not have a significant influence on its formation, as experiments with sodium as the cation have shown. An analogous silicate-cyclodextrin adduct is even obtained from sodium hydroxide solution; however, in the homologous sodium compound, the potential cation binding sites next to the prism bases are only partly occupied by sodium ions, while other positions remain free from cations (which in this case are unfavorably small).
14. -O-Si hydrogen bonds. The acidity of polysilicic acids is discussed in: A. F. Holleman, E. Wiberg, N. Wiberg, Lehrbuch der Anorganischen Chemie, de Gruyter, Berlin, 1995, p. 924ff.
15. a) P. Klüfers, H. Piotrowski, J. Uhlendorf, Chem. Eur. J., 1997, 3, 601-608;
16. b) P. Klüfers, J. Schuhmacher, Angew. Chem. 1994, 106, 1925-1927; Angew. Chem. Int. Ed. Engl. 1994, 33, 1863-1865;
17. b) P. Klüfers, J. Schuhmacher, Angew. Chem. 1994, 106, 1925-1927; Angew. Chem. Int. Ed. Engl. 1994, 33, 1863-1865;
18. c) R. Fuchs, N. Habermann, P. Klüfers, ibid. 1993, 105, 895-897 and 1993, 32, 852-854.
19. c) R. Fuchs, N. Habermann, P. Klüfers, ibid. 1993, 105, 895-897 and 1993, 32, 852-854.
20. D. Philp, J. F. Stoddart, Angew. Chem. 1996, 108, 1243-1286; Angew. Chem. Int. Ed. Engl. 1996, 35, 1154-1196, look upon cyclodextrins as building blocks of low information content, since they base their judgement on the less specific host-guest chemistry of the cyclodextrins and not on the specific pattern of functional groups.
21. D. Philp, J. F. Stoddart, Angew. Chem. 1996, 108, 1243-1286; Angew. Chem. Int. Ed. Engl. 1996, 35, 1154-1196, look upon cyclodextrins as building blocks of low information content, since they base their judgement on the less specific host-guest chemistry of the cyclodextrins and not on the specific pattern of functional groups.