Dynamic NMR Determination of the Barrier for Interconversion of the Left- and Right-Handed Helical Conformations in a Polyisocyanate

Macromolecules

Volumn 32, Issue 4, 1999, Pages 1304-1307

  Ute, Koichi ^a   Fukunishi, Yoichi ^a   Jha, Salil K ^b   Cheon, Kap Soo ^b   Muñoz, Beth ^b   Hatada, Koichi ^a   Green, Mark M ^b  

^a OSAKA UNIVERSITY   (Japan)

^b POLYTECHNIC UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CONFORMATIONS; MOLECULAR STRUCTURE; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; THERMAL EFFECTS;

BARRIER ENERGY; POLYISOCYANATE;

POLYESTERS;

EID: 0033076956     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma981427h     Document Type: Article

References (35)

1. Green, M. M.; Peterson, N. C.; Sato, T.; Teramoto, A.; Cook, R.; Lifson, S. Science 1995, 268, 1860.
2. Lifson, S.; Felder, C. E.; Green, M. M. Macromolecules 1992, 25, 4142. For a recent demonstration of this structure, see: Maeda, K.; Okamoto, Y. Macromolecules 1998, 31, 5164.
3. Lifson, S.; Felder, C. E.; Green, M. M. Macromolecules 1992, 25, 4142. For a recent demonstration of this structure, see: Maeda, K.; Okamoto, Y. Macromolecules 1998, 31, 5164.
4. (a) Lifson, S.; Andreola, C.; Peterson, N. C.; Green, M. M. J. Am. Chem. Soc. 1989, 111, 8850.
5. (b) Selinger, J. V.; Selinger, R. L. B. Phys. Rev. Lett. 1996, 76, 58.
6. (c) Selinger, J. V.; Selinger, R. L. B. Phys. Rev. E 1997, 55, 1728.
7. (d) Gu, H.; Sato, T.; Teramoto, A.; Varichon, L.; Green, M. M. Polym. J. 1997, 29, 77.
8. Gu, H.; Nakamura, Y.; Sato, T.; Teramoto, A.; Green, M. M.; Andreola, C.; Peterson, N. C.; Lifson, S. Macromolecules 1995, 28, 1016. Okamoto, N.; Mukaida, F.; Gu, H.; Nakamura, Y.; Sato, T.; Teramoto, A.; Green, M. M.; Andreola, C.; Peterson, N. C.; Lifson, S. Macromolecules 1996, 29, 2878.
9. Gu, H.; Nakamura, Y.; Sato, T.; Teramoto, A.; Green, M. M.; Andreola, C.; Peterson, N. C.; Lifson, S. Macromolecules 1995, 28, 1016. Okamoto, N.; Mukaida, F.; Gu, H.; Nakamura, Y.; Sato, T.; Teramoto, A.; Green, M. M.; Andreola, C.; Peterson, N. C.; Lifson, S. Macromolecules 1996, 29, 2878.
10. Mislow, K.; Raban, M. Top. Stereochem. 1967, 1, 1.
11. Pople, J. A.; Schneider, W. G.; Bernstein, H. J. High-Resolution Nuclear Magnetic Resonance; McGraw-Hill: New York, 1959; Chapter 10.
12. Line width measurements on poly(n-hexyl isocyanate) have been used to study the effect of local segmental motions on global dimensional properties. See: Cook, R.; Johnson, R. D.; Wade, C. G.; O'Leary, D. J.; Munoz, B.; Green, M. M. Macromolecules 1990, 23, 3454.
13. (a) See ref 3c.
14. (b) Jha, S. K.; Cheon, K. S.; Green, M. M.; Selinger, J. V. J. Am. Chem. Soc., in press.
15. This information may have technological benefits in the use of these polymers for the amplification of the small enantiomeric excesses produced by photoresolution. See: Dagani, R. Chem. Eng. News 1996, September 23, 17. For leading references, please see: Schuster, G. B.; Zhang, M. J. Am. Chem. Soc. 1994, 116, 4852. Suarez, M.; Schuster, G. B. J. Am. Chem. Soc. 1995, 117, 6732. Huck, N. P. M.; Jager, W. F.; de Lange, B.; Feringa, B. L. Science 1996, 273, 1686.
16. This information may have technological benefits in the use of these polymers for the amplification of the small enantiomeric excesses produced by photoresolution. See: Dagani, R. Chem. Eng. News 1996, September 23, 17. For leading references, please see: Schuster, G. B.; Zhang, M. J. Am. Chem. Soc. 1994, 116, 4852. Suarez, M.; Schuster, G. B. J. Am. Chem. Soc. 1995, 117, 6732. Huck, N. P. M.; Jager, W. F.; de Lange, B.; Feringa, B. L. Science 1996, 273, 1686.
17. This information may have technological benefits in the use of these polymers for the amplification of the small enantiomeric excesses produced by photoresolution. See: Dagani, R. Chem. Eng. News 1996, September 23, 17. For leading references, please see: Schuster, G. B.; Zhang, M. J. Am. Chem. Soc. 1994, 116, 4852. Suarez, M.; Schuster, G. B. J. Am. Chem. Soc. 1995, 117, 6732. Huck, N. P. M.; Jager, W. F.; de Lange, B.; Feringa, B. L. Science 1996, 273, 1686.
18. This information may have technological benefits in the use of these polymers for the amplification of the small enantiomeric excesses produced by photoresolution. See: Dagani, R. Chem. Eng. News 1996, September 23, 17. For leading references, please see: Schuster, G. B.; Zhang, M. J. Am. Chem. Soc. 1994, 116, 4852. Suarez, M.; Schuster, G. B. J. Am. Chem. Soc. 1995, 117, 6732. Huck, N. P. M.; Jager, W. F.; de Lange, B.; Feringa, B. L. Science 1996, 273, 1686.
19. For an example in which NMR has been used to study the interconversion of helical sense in an oligomer, see: Ute, K.; Hirose, K.; Kashimoto, H.; Hatada, K.; Vogl, O. J. Am. Chem. Soc. 1991, 113, 6305. Ute, K.; Hirose, K.; Kashimoto, H.; Nakayama, H.; Hatada, K.; Vogl, O. Polym. J. 1993, 25, 1175.
20. For an example in which NMR has been used to study the interconversion of helical sense in an oligomer, see: Ute, K.; Hirose, K.; Kashimoto, H.; Hatada, K.; Vogl, O. J. Am. Chem. Soc. 1991, 113, 6305. Ute, K.; Hirose, K.; Kashimoto, H.; Nakayama, H.; Hatada, K.; Vogl, O. Polym. J. 1993, 25, 1175.
21. For synthetic detail of the preparation of 2-butylhexyl isocyanate and the derived polymer, see: Munoz, B.; Jha, S. K. Doctoral Theses, Polytechnic University, Brooklyn, New York, 1993 and 1998 respectively and ref 8b.
22. n = 2.73.
23. For discussion of the thermal decomposition of the polyisocyanates and leading references, see; Ute, K.; Asai, T.; Fukunishi, Y.; Hatada, K. Polym. J. 1995, 27, 445.
24. Jeener, J.; Meier, B. H.; Bachmann, P.; Ernst, R. R. J. Chem. Phys. 1979, 71, 4546.
25. See ref 8b and Jha, S. K. in ref 11. The 2-butylhexyl side chain units far exceed the amplification characteristics of the n-hexyl groups first reported in these sergeants and soldiers copolymers; see: Green, M. M.; Reidy, M. P.; Johnson, R. D.; Darling, G.; O'Leary, D. J.; Willson, G. J. Am. Chem. Soc. 1989, 111, 6452.
26. Force field work in progress with R. Cook of Lawrence Livermore National Laboratories. A quantum mechanical approach with Monte Carlo simulations is underway with C. Aleman, Universitat Politecnica de Catalunya, Spain.
27. Ute, K.; Asada, T.; Nabeshima, Y.; Hatada, K. Acta Polym. 1995, 46, 458.
28. Okamoto, Y.; Mohri, H.; Nakano, T.; Hatada, K. J. Am. Chem. Soc. 1989, 111, 5952.
29. Mohri, H. Doctoral Dissertation, Osaka University, Osaka, Japan, 1989.
30. Schlitzer, D. S.; Novak, B. M. J. Am. Chem. Soc. 1998, 120, 2196. The barrier energy reported in this work of only 6.4 kcal/mol seems too small for the laboratory time scale observation.
31. 13C) = 2.00 ppm] as an internal standard and converted to the TMS scale.
32. Guenet, J. M.; Jeon, H. S. J.; Khatri, C.; Jha, S. K.; Balsara, N. P.; Green, M. M.; Brulet, A.; Thierry, A. Macromolecules 1997, 30, 4590.
33. Green, M. M.; Zanella, S.; Gu, H.; Sato, T.; Gottarelli, G.; Jha, S. K.; Spada, G. P.; Schoevaars, A. M.; Feringa, B.; Teramoto, A. J. Am. Chem. Soc. 1998, 120, 9810.
34. Park, J. W.; Green, M. M. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 1998, 39 (2), 707.
35. See also: Muellers, B. T.; Green, M. M.; Brookhart, M. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 1998, 39 (2), 709.