Self-organization of a heteroditopic molecule to linear polymolecular arrays in solution

Angewandte Chemie - International Edition

Volumn 37, Issue 17, 1998, Pages 2361-2364

  Yamaguchi, Nori ^a   Nagvekar, Devdatt S ^a   Gibson, Harry W ^a  

^a VIRGINIA POLYTECHNIC INSTITUTE AND STATE UNIVERSITY   (United States)

Author keywords

Crown compounds; Noncovalent interactions; Rotaxanes; Self organization; Supramolecular chemistry

Indexed keywords

EID: 0032544461     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(19980918)37:17<2361::AID-ANIE2361>3.0.CO;2-P     Document Type: Article

References (32)

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19. For the self-organization of a monosubstituted β-cyclodextrin to a polymeric array in the solid state where the tert-butylsulfonyl group is intermolecularly included in the cavity of the cyclodextrin, sec : K. Hirotsu, T. Higuchi, K. Fujita, T. Ueda, A. Shinoda, T. Imoto, I. Tabushi, J. Org. Chem. 1982, 47, 1143-1144. Indeed, as early as 1977 Cram et al. suggested the formation of polymeric species by complexation of bis(crown ethers) and α,ω-diammonium salts: R. C. Helgeson, T. L. Tarnowski, J. M. Timko, D. J. Cram, J. Am. Chem. Soc. 1977, 99, 6411-6418.
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22. o, p was calculated.
23. 1H NMR data.
24. f.
25. The expression n=1/(1-p) assumes that the cyclic species do not contribute to consumption of host and guest sites. In covalent polymer chemistry it is well understood that the percentage of cyclic molecules of any size formed at high concentrations (e.g., 1.0M) is very small indeed (<3%) and that linear macromolecules are preferentially formed. For reviews on cyclization versus linear polymerization, see: a) G. Odian, Principles of Polymerization, 3rd ed., Wiley, New York, 1991, p. 73; b) S. C. Hamilton, J. A. Semlyen, Polymer. 1997, 38, 1685-1691. Therefore, the assumption that the absence of cyclic complexes dramatically increases with concentration is validated.
26. The expression n=1/(1-p) assumes that the cyclic species do not contribute to consumption of host and guest sites. In covalent polymer chemistry it is well understood that the percentage of cyclic molecules of any size formed at high concentrations (e.g., 1.0M) is very small indeed (<3%) and that linear macromolecules are preferentially formed. For reviews on cyclization versus linear polymerization, see: a) G. Odian, Principles of Polymerization, 3rd ed., Wiley, New York, 1991, p. 73; b) S. C. Hamilton, J. A. Semlyen, Polymer. 1997, 38, 1685-1691. Therefore, the assumption that the absence of cyclic complexes dramatically increases with concentration is validated.
27. S. Glasstone, D. Lewis, Elements of Physical Chemistry, 2nd ed., Van Nostrand, New York, 1960, pp. 597-598.
28. Not surprisingly, fibers could be pulled from very concentrated solutions in acetone (>2.0.M). This observation is indicative of significant linear array extension in the material, consequently giving rise to polymeric properties.
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31. g observed at -20°C down to slightly above the freezing temperature of the solvent (-94°C) were unchanged at δ-5.944 and 5.862, which correspond to n values of 4.3 and 14, respectively.
32. +, respectively.