Intramolecular Cross-Linking of Helical Folds: An Approach to Organic Nanotubes

Angewandte Chemie - International Edition

Volumn 42, Issue 48, 2003, Pages 6021-6024

  Hecht, Stefan ^a   Khan, Anzar ^a  

^a FREIE UNIVERSITÄT BERLIN   (Germany)

Author keywords

Cross linking; Helical structures; Materials science; Nanotubes; Topochemistry

Indexed keywords

CROSSLINKING; DERIVATIVES; DIMERIZATION; ETHYLENE;

PHOTODIMERIZATION;

NANOTUBES;

BENZENE DERIVATIVE; ORGANIC COMPOUND; POLY(3 PHENYLENEETHYNYLENE) DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CROSS LINKING; DIMERIZATION; NANOPARTICLE; NANOTECHNOLOGY; NANOTUBE; PROCESS DESIGN; STRUCTURE ANALYSIS;

EID: 0347985382     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200352983     Document Type: Article

References (41)

1. For a comprehensive review on organic nanotubes, see D.T. Bong, T. D. Clark, J. R. Granja, M. R. Ghadiri, Angew. Chem. 2001, 113, 1016-1041; Angew. Chem. Int. Ed. 2001, 40, 988-1011.
2. For a comprehensive review on organic nanotubes, see D.T. Bong, T. D. Clark, J. R. Granja, M. R. Ghadiri, Angew. Chem. 2001, 113, 1016-1041; Angew. Chem. Int. Ed. 2001, 40, 988-1011.
3. For a recent review on inorganic nanostructures, see Y. Xia, P. Yang, Y. Sun, Y. Wu, B. Mayers, B. Gates, Y. Yin, F. Kim, H. Yan, Adv. Mater. 2003, 15, 353-389.
4. For a review on regioselectively cross-linked nanostructures, see C. G. Clark, K. L. Wooley in Dendrimers and other Dendritic Polymers (Eds.: J.M.J. Fréchet, D. A. Tomalia), Wiley, Chichester, 2001, pp. 147-170.
5. Recently, hollow tubes were generated using peripheral cross-linking of dendronized oligomers followed by removal of the inner core: a) Y. Kim, M. E. Mayer, S. C. Zimmerman, Angew. Chem. 2003, 115, 1153-1158; Angew. Chem. Int. Ed. 2003, 42, 1121-1126.
6. Recently, hollow tubes were generated using peripheral cross-linking of dendronized oligomers followed by removal of the inner core: a) Y. Kim, M. E. Mayer, S. C. Zimmerman, Angew. Chem. 2003, 115, 1153-1158; Angew. Chem. Int. Ed. 2003, 42, 1121-1126.
7. This approach is related to the concept of cored dendrimers: b) M. S. Wendland, S. C. Zimmerman, J. Am. Chem. Soc. 1999, 121, 1389-1390.
8. Short α-helical peptides (without an internal void) have been stabilized by a single covalent cross-link: a) H. E. Blackwell, R.H. Grubbs, Angew. Chem. 1998, 110, 3469-3472; Angew. Chem. Int. Ed. 1998, 37, 3281-3284,
9. Short α-helical peptides (without an internal void) have been stabilized by a single covalent cross-link: a) H. E. Blackwell, R.H. Grubbs, Angew. Chem. 1998, 110, 3469-3472; Angew. Chem. Int. Ed. 1998, 37, 3281-3284,
10. or their conformation switched using a single azobenzene linker: b) J. R. Kumita, O. S. Smart, G. A. Woolley, Proc. Natl. Acad. Sci. USA 2000, 97, 3803-3808;
11. c) D. G. Flint, J. R. Kumita, O. S. Smart, G.A. Woolley, Chem. Biol. 2002, 9, 391-397.
12. For a comprehensive review on foldamers, see a) D. J. Hill, M. J. Mio, R. B. Prince, T. S. Hughes, J. S. Moore, Chem. Rev. 2001, 101, 3893-4011;
13. for a review on synthetic helical polymers, see b) T. Nakano, Y. Okamoto, Chem. Rev. 2001, 101, 4013-4038;
14. for a review on supramolecular helical architectures, see c) J. J. L. M. Cornelissen, A. E. Rowan, R. J. M. Nolte, N. A. J. M. Sommerdijk, Chem. Rev. 2001, 101, 4039-4070.
15. For a comprehensive review about poly(phenyleneethynylene)s, mostly of the para-type, see U. H. F. Bunz, Chem. Rev. 2000, 100, 1605-1644.
16. a) J. C. Nelson, J. G. Saven, J. S. Moore, P. G. Wolynes, Science 1997, 277, 1793-1796;
17. b) R. B. Prince, J.G. Saven, P. G. Wolynes, J. S. Moore, J. Am. Chem. Soc. 1999, 121, 3114-3121;
18. c) R. B. Prince, PhD thesis thesis, University of Illinois (Urbana-Champaign), 2000.
19. The 6-helix is defined as a helix having six repeat units per turn. Experimental evidence for this structure arises from ESR double spin labeling experiments: K. Matsuda, M. T. Stone, J. S. Moore, J. Am. Chem. Soc. 2002, 124, 11836-11837.
20. For a review on topochemical [2+2] photodimerization of cinnamates, see a) G. M. J. Schmidt, Pure Appl. Chem. 1971, 27, 647-678;
21. for an example in a two-dimensional crystal, that is, on a surface, see b) M. M. S. Abdel-Mottaleb, S. De Feyter, A. Gesquiere, M. Sieffert, M. Klapper, K. Müllen, F. C. De Schryver, Nano Lett. 2001, 1, 353-357;
22. for an example in a liquid-crystalline phase, see c) C. Mertesdorf, H. Ringsdorf, J. Stumpe, Liq. Cryst. 1991, 9, 337-357.
23. The preparation of polymers from di-olefinic monomers by [2+2] photodimerization has been reviewed in: a) W. L. Dilling, Chem. Rev. 1983, 83, 1-47;
24. b) M. Hasegawa, Chem. Rev. 1983, 83, 507-518.
25. This is related to the topochemical principle: a) V. Kohlschütter, Z. Anorg. Allg. Chem. 1918, 105, 1-25;
26. for a comprehensive review, see b) V. Ramamurthy, K. Venkatesan, Chem. Rev. 1987, 87, 433-481.
27. A. Khan, S. Hecht, unpublished results. For related approaches, see a) V. A. Solomin, W. Heitz, Macromol. Chem. Phys. 1994, 195, 303-314;
28. A. Khan, S. Hecht, unpublished results. For related approaches, see a) V. A. Solomin, W. Heitz, Macromol. Chem. Phys. 1994, 195, 303-314;
29. b) H. Haeger, W. Heitz, Macromol. Chem. Phys. 1998, 199, 1821-1826;
30. the in situ deprotection/coupling conditions are inspired by: c) M. J. Mio, L. C. Kopel, J. B. Braun, T. L. Gadzikwa, K. L. Hull, R. G. Brisbois, C. J. Markworth, P. A. Grieco, Org. Lett. 2002, 4, 3199-3202.
31. According to optical spectroscopy, the molecular weight determined by GPC is most likely underestimated (see Figure 2).
32. See the Supporting Information.
33. B. H. Zimm, J. K. Bragg, J. Chem. Phys. 1959, 31, 526-533.
34. D. J. Hill, J. S. Moore, Proc. Natl. Acad. Sci. USA 2002, 99, 5053-5057.
35. In bulk cinnamate phases, β- and δ-truxinates (syn and anti head-head photodimers) constitute the major photodimerization products: P. L. Egerton, E. M. Hyde, J. Trigg, A. Payne, P. Beynon, M. V. Mijovic, A. Reiser, J. Am. Chem. Soc. 1981, 103, 3859-3863.
36. D.A. Ben-Efraim, B.S. Green, Tetrahedron 1974, 30, 2357-2364; F. D. Lewis, S. L. Quillen, P. D. Hale, J. D. Oxman, J. Am. Chem. Soc. 1988, 110, 1261-1267.
37. D.A. Ben-Efraim, B.S. Green, Tetrahedron 1974, 30, 2357-2364; F. D. Lewis, S. L. Quillen, P. D. Hale, J. D. Oxman, J. Am. Chem. Soc. 1988, 110, 1261-1267.
38. Strong upfield chemical shifts upon transition to the folded helical structure have been reported in reference [8a] and S. Lahiri, J. L. Thompson, J. S. Moore, J. Am. Chem. Soc. 2000, 122, 11315-11319.
39. Visualization attempts using STM and TEM have so far been unsuccessful because of the significant thickness (low tunneling current) and the low contrast (all carbon material), respectively, of the tubes.
40. The outer and inner diameters are encoded in the foldamer motif used. Length control-currently not possible by means of self-assembly-could be achieved using a folding polymer of low polydispersity prepared by advanced living polymerization techniques.
41. In principle the use of heterosequences (alternating as well as block copolymers) enables nonstatistical, location-specific outer/ inner functionalization. Currently, such control over surface chemistry cannot be realized in carbon or inorganic nanotubes