[en] The synthesis, characterization, and self-assembly in butanol of a series of well-defined a,a'-linked quinqui-, sexi-, and septithiophenes substituted, via ester links at their termini, by chiral oligo(ethylene oxide) chains carrying an a, ß, d, and e methyl, respectively, are reported. Studies of the self-assembly of these molecules using UV/visible absorption, luminescence, and circular dichroism spectroscopies reveal, for the sexithiophene case, that the magnitude of the observed Cotton effect in the aggregates diminishes progressively as the chiral substituent is moved away from the thiophene segment. The stability of the assemblies increases with the length of the oligothiophene and as the substituent chiral unit is moved away from the aromatic core, being greatest for the unsubstituted case. The sign of the Cotton effect alternates in an 'odd/even' manner as the position of the chiral substituent is moved along the oligo(ethylene oxide) chain and on going from the quinquethiophene to the septithiophene having the same side chain. Atomic force microscopy on materials deposited from solution on an aluminum or glass surface and optical measurements show that capsules are formed from the oligothiophenes with H-type packing of the aromatic segments.
Disciplines :
Chemistry Physics
Author, co-author :
Henze, O.
Feast, W.J.
Gardebien, F.
Jonkheijm, P.
Lazzaroni, Roberto ; Université de Mons > Faculté des Sciences > Service de Chimie des matériaux nouveaux
Leclère, Philippe ; Université de Mons > Faculté des Sciences > Chimie des matériaux nouveaux
Meijer, E.W.
Schenning, A.P.H.J.
Language :
English
Title :
Chiral Amphiphilic Self-Assembled a,a'-Linked Quinque-, Sexi-, and Septithiophenes: Synthesis, Stability and Odd-Even Effects
Publication date :
03 May 2006
Journal title :
Journal of the American Chemical Society
ISSN :
0002-7863
Publisher :
American Chemical Society, United States - District of Columbia
Volume :
128
Issue :
17
Pages :
5923-5929
Peer reviewed :
Peer Reviewed verified by ORBi
Research unit :
S817 - Chimie des matériaux nouveaux
Research institute :
R400 - Institut de Recherche en Science et Ingénierie des Matériaux
Circular Dichroic Spectroscopy; Harada, N., Nakanishi, K., Eds.; University Science Books: Mill Valley, CA, USA; Oxford University Press: Oxford, 1983.
Hoeben, F. J. M.; Jonkheijm, P. Meijer, E. W.; Schenning, A. P. H. J. Chem. Rev. 2005, 105, 1491.
Langeveld-Voss, B. M. W.; Beljonne, D.; Shuai, Z.; Janssen, R. A. J.; Meskers, S. C. J.; Meijer, E. W.; Brédas, J. L. Adv. Mater. 1998, 10, 1343.
Lermo, E. R.; Langeveld-Voss, B. M. W.; Janssen, R. A. J.; Meijer, E. W. Chem. Commun. 1999, 791.
The properties of T6βS and T6 have been reported earlier: (a) Kilbinger, A. F. M.; Schenning, A. P. H. J.; Goldoni, F.; Feast, W. J.; Meijer, E. W. J. Am. Chem. Soc. 2000, 122, 1820.
(b) Schenning, A. P. H. J.; Kilbinger, A. F. M.; Biscarini, F.; Cavallini, M.; Cooper, H. J.; Derrick, P. J.; Feast, W. J.; Lazzaroni, R.; Leclere, Ph.; McDonell, L. A.; Meijer, E. W.; Meskers, S. C. J. J. Am. Chem. Soc. 2002, 124, 1269.
(a) Gray, G. W.; McDonell, D. G. Mol. Cryst. Liq. Cryst. 1977, 34, 211.
(b) Goodby, J. W.; Chin, E.; Leslie, T. M.; Geary, J. M.; Patel, J. S. J. Am. Chem. Soc. 1986, 108, 4729.
(c) Goodby, J. W., Gray, G. W., Spiess. H.-W., Vill, V., Eds.; Handbook of Liquid Crystals; Wiley-VCH: Weinheim. 1998.
(a) Ramos, E.; Bosch, J.; Serrano, J.-L.; Sierra, T.; Veciana, J. J. Am. Chem. Soc. 1996, 108, 4729.
(b) Amabilino, B.; Ramos, E.; Serrano, J. L.; Veciana, J. Adv. Mater. 1998, 10, 1001.
(c) Amabilino, B.; Ramos, E.; Serrano, J.-L.; Sierra, T.; Veciana, J. J. Am. Chem. Soc. 1998, 120, 9126.
For example: (a) Aoki, K.; Kudo, M.; Tamaoki, N. Org. Lett. 2004, 6, 4009.
(c) Ishi-I, T.; Iguchi, R.; Snip, I.; Ikeda, M.; Shinkai, S. Langmuir 2001, 17, 5825.
(d) Li, Y.; Li, P.; Wang, J.; Wang, Y.; Yan, H.; Thomas, R. K. Langmuir 2005, 21, 6703.
(e) Sumiyoshi, Y.; Nishimura, K.; Nakano, M.; Handa, T.; Miwa, Y.; Tomioka, K. J. Am. Chem. Soc. 2003, 125, 12137.
An odd-even effect concerning the position of chiral center has been observed in the circular dichroism spectrum of polyfluorene films: Oda, M.; Nothofer, H.-G.; Scherf, U.; Sunjic, V.; Richter, D.; Regenstein, W.; Neher, D. Macromolecules 2002, 35, 6792.
Shklyarevskiy, I. O.; Jonkheijm, P.; Christianen, P.; Schenning, A. P. H. J.; Meijer, E. W.; Henze, O.; Kilbinger, A. F. M.; Feast, W. J.; de Guerzo, A.; Desvergne, J.; Maan, J. C. J. Am. Chem. Soc. 2005, 127, 1112.
Leclere, Ph.; Surin, M.; Lazzaroni, R.; Kilbinger, A. F. M.; Henze, O.; Jonkheijm, P.; Biscarini, F.; Cavallini, M.; Feast, W. J.; Meijer, E. W.; Schenning, A. P. H. J. J. Mater. Chem. 2004, 14, 1959.
Janssen, H. M.; Peeters, E.; v. Zundert, M. F.; v. Genderen, M. H. R: Meijer, E. W. Macromolecules 1997, 30, 8113.
(a) Mori, K. Tetrahedron 1976, 32, 1101.
(b) Perkins, M. V.; Kitching, W.; Köning, W. A.; Drew, R. A. I. J. Chem. Soc., Perkin Trans. 1 1990, 2501.
(c) Cowie, J. M. G.; Hunter, H. W. Makromol. Chem. 1990, 191, 1393.
(f) Parakka, J. P.; Cava, M. P. Tetrahedron 1995, 51, 2229.
Kawano, S.-i.; Fujita, N.; Shinkai, S. Chem.-Eur. J. 2005, 11, 4735.
Jonkheijm, P.; Hoeben, F. J. M.; Kleppinger, R.; van Herrikhuyzen, J.; Schenning, A. P. H. J.; Meijer, E. W. J. Am. Chem. Soc. 2003, 125, 15941.
Meinardi, F.; Cerminara, M.; Borghesi, A.; Spearman, P.; Bongionvanni, G.; Mura, A.; Tubino, R. Phys. Rev. Lett. 2002, 89, 157403-1
Kouki, F. J. Chem. Phys. 2000, 113, 385.
The values are high for π-π interactions which points to additional secondary interactions such as side chain association.
(a) Jiang, L.; Hughes, R. C.; Sasaki, D. Y. Chem. Commun. 2004, 1028.
(b) Hoeben, F. J. M.; Shklyarevskiy, I. O.; Pouderoijen, M. J.; Engelkamp, H.; Schenning, A. P. H. J.; Christianen, P. C. M.; Maan, J. C.; Meijer E. W. Angew. Chem., Int. Ed. 2006, 45, 1232.
