[en] The self-organization behavior of an amphiphilic sexithiophene bearing amide functionalities is studied and compared to that of a deriv. bearing an ester group at the same position. The introduction of hydrogen-bond interactions in assemblies of these pi-conjugated oligomers is found to affect the mol. organization both in protic media and in thin deposits on mica. The amphiphilic 2,2';5',2'';5'',2''';5''',2''''; 5'''',2'''''-sexithiophene-5,5'''''-dicarboxylic acid bis[(4,7,10,13,16-pentaoxaheptadecyl)amide] forms assemblies in n-butanol and water and partially aggregates in toluene. Spectroscopy reveals that the presence of a hydrogen-bonding moiety increases the thermal stability of the assemblies in n-butanol and even more in water soln. On mica surfaces, the formation of rod-like one-dimensional nano-structures is obsd. after deposition from toluene solns. In addn., transmission electron microscopy in combination with selected area electron diffraction shows that in water plate-like structures are formed built from parallel oriented stacks, with a pi-pi distance of 3.5 .ANG.. Comparison of these data to mol. modeling and quantum chem. calcns. is used to better understand the influence of the amide group on the stacking of these compds. The introduction of these H-bonding interactions leads to denser and more stable stacks. Furthermore, we show that a deriv. of the amide compd., bearing terminal ammonium groups, forms a complex with chiral polyanions in aq. media such that the sexithiophene segments are stacked in a meta-stable helical fashion with preferred handedness. We obsd. that poly(glutamate) and DNA generate a chiral sexithiophene assembly. In time the induced chirality disappears, which is explained by the meta-stability of the kinetically formed adduct. This constitutes one step forward towards the controlled formation of functional multi-component systems in aq. soln. [on SciFinder (R)]
Disciplines :
Chemistry Physics
Author, co-author :
Brustolin, F.
Surin, Mathieu ; Université de Mons > Faculté des Sciences > Chimie des matériaux nouveaux
Lemaur, Vincent ; Université de Mons > Faculté des Sciences > Chimie des matériaux nouveaux
(a) Electronic Materials: The Oligomer Approach, ed. by K. Mullen, G. Wegner, Wiley-VCH, Weinheim, Germany, 1998.
(b) D. Fichou, J. Mater. Chem., 2000, 10, 571.
(c) F. Gamier, G. Horowitz, X. Peng, D. Fichou, Adv. Mater. 1990, 2, 592.
(d) G. Horowitz, D. Fichou, X. Peng, Z. Xu, F. Gamier, Solid State Commun. 1989, 72, 381.
(e) F. J. M. Hoeben, P. Jonkheijm, E. W. Meijer, A. P. H. J. Schenning, Chem. Rev. 2005, 705, 1491.
(f) M. R. Wasielewski, J. Org. Chem. 2006, 71, 5051.
(g) J. A. A. W. Elemans, R. van Hameren, R. J. M. Nolte, A. E. Rowan, Adv. Mater. 2006, 18, 1251.
(a) H. E. Katz, J. G. Laquindanum, A. J. Lovinger, Chem. Mater. 1998, 10, 633.
(b) H. E. Katz, J. Mater. Chem. 1997, 7,369.
(c) H. E. Katz, A. Dodabalapur, L. Torsi, D. Elder, Chem. Mater. 1995, 7, 2238.
(d) J. P. Parakka, M. P. Cava, Tetrahedron 1995, 51, 2229.
(e) F. Garnier, A. Yassar, R. Hajlaoui, G. Horowitz, F. Deloffre, B. Servet, S. Ries, P. Alnot, J. Am. Chem. Soc. 1993, 115, 8716.
(f) A. R. Murphy, P. C. Chang, P. VanDyke, J. Liu, J. M. J. Fréchet, V. Subramanian, D. M. DeLongchamp, S. Sambasivan, D. A. Fisher, E. K. Lin, Chem. Mater. 2005, 17, 6033.
(g) A. Dell'Aquila, P. Mastrorilli, C. F. Nobile, G. Romanazzi, G. P. Suranna, L. Torsi, M. C. Tanese, D. Acierno, E. Amendola, P. Morales, J. Mater. Chem. 2006, 16, 1183.
(h) G. Zotti, S. Zecchin, B. Vercelli, M. Pasini, S. Destri, F. Bertini, A. Berlin, Chem, Mater. 2006, 18, 3151.
(a) F. Brustolin, F. Goldoni, E. W. Meijer, N. A. J. M. Sommerdijk, Macromolecules 2002, 35, 1054.
(b) T. Bjørnholm, D. R. Greve, N. Reitzel, T. Hassnkam, K. Kjaer, P. B. Howes, N. B. Larsen, J. Bøgelund, M. Jayaraman, P. C. Ewbank, R. D. McCullough, J. Am. Chem. Soc. 1998, 120, 7643.
(c) L. Belobrzeckaja, G. Bajo, A. Bolognesi, M. Catellani, Synth. Met. 1997, 84, 195.
(d) R. D. McCullough, S. P. Williams, Chem. Mater. 1995, 7, 2001.
(e) I. Lévesque, M. Leclerc, J. Chem. Soc. Chem. Commun. 1995, 2293.
(f) I. Lévesque, M. Leclerc, Chem. Mater. 1996, 8, 2843.
(g) R. D. McCullough, S. P. Williams, J. Am. Chem. Soc. 1993, 115, 11608.
(h) J. H. Wosnick, C. M. Mello, T. M. Swager, J. Am. Chem. Soc. 2005, 127, 3400.
(i) G. Angelini, C. Cusan, P. De Maria, A. Fontana, M. Maggini, M. Pierini, M. Prato, S. Schergna, C. Villani, Eur. J. Org. Chem. 2005, 1884.
(j) Z. Gu, Y.-J. Bao, Y. Zhang, M. Wang, Q.-D. Shen, Macromolecules 2006, 39, 3125.
(a) A. F. M. Kilbinger, A. P. H. J. Schenning, F. Goldoni, W. J. Feast, E. W. Meijer, J. Am. Chem. Soc. 2000, 122, 1820.
(b) A. P. H. J. Schenning, A. F. M. Kilbinger, F. Biscarini, M. Cavallini, H. J. Cooper, P. J. Derrick, W. J. Feast, R. Lazzaroni, Ph. Leclère, L. A. McDonnel, E. W. Meijer, S. C. J. Meskers, J. Am. Chem. Soc. 2002, 124, 1269.
(c) O. Henze, W. J. Feast, F. Gardebien, P. Jonkheijm, R. Lazzaroni, P. Leclere, E. W. Meijer, A. P. H. J. Schenning, J. Am, Chem. Soc. 2006, 128, 5923.
C. Xia, J. Locklin, J. H. Touk, T. Fulghum, R. C. Advincula, Langmuir 2002, 18, 955.
(a) P. Jonkheijm, M. Fransen, A. P. H. J. Schenning, E. W. Meijer, J. Chem. Soc., Perkin Trans. 2 2001, 1280.
(b) V. Urban, H. H. Wang, P. Thiyagarajan, K. C. Littrell, H. B. Wang, L. Yu, J. Appl. Crystallogr. 2000, 33, 645.
(c) H. Xiong, L. Qin, J. Sun, X. Zhang, J. Shen, Chem. Lett. 2000, 586.
B. S. Gaylord, S. Wang, A. J. Heeger, G. C. Bazan, J. Am. Chem. Soc. 2001, 123, 6417.
(a) R. Nonokawa, E. Yashima, J. Am. Chem. Soc. 2003, 125, 1278.
(b) E. Yashima, K. Maeda, O. Sato, J. Am. Chem. Soc. 2001, 123, 8159.
K. Akagi, G. Piao, S. Kaneko, K. Sakamaki, H. Shirakawa, M. Kyotani, Science 1998, 282, 1683.
(a) R. B. Prince, L. Brunsveld, E. W. Meijer, J. S. Moore, Angew. Chem., Int. Ed. 2000, 39, 228.
(b) A. F. M. Kilbinger, A. P. H. J. Schenning, F. Goldoni, W. J. Feast, E. W. Meijer, J. Am. Chem. Soc. 2000, 122, 1820.
(a) L. Brunsveld, E. W. Meijer, R. B. Prince, J. S. Moore, J. Am. Chem. Soc. 2001, 123, 7978.
(b) R. B. Prince, J. S. Moore, L. Brunsveld, E. W. Meijer, Chem.-Eur. J. 2001, 7, 4150.
(a) P. Breccia, M. Van Gool, R. Pérez-Fernández, S. Martín-Santamaría, F. Gago, P. Prados, J. de Mendoza, J. Am. Chem. Soc. 2003, 125, 8270.
(b) H. Onouchi, T. Miyagawa, K. Morino, E. Yashima, Angew. Chem., Int. Ed. 2006, 45, 2381.
(c) S.-I. Sakurai, K. Okoshi, J. Kumaki, E. Yashima, J. Am. Chem. Soc. 2006, 128, 5650.
(a) H. Fenniri, B.-L. Deng, A. E. Ribbe, J. Am. Chem. Soc. 2002, 124, 11064.
(b) A. Tanatani, M. J. Mio, J. S. Moore, J. Am. Chem. Soc. 2001, 123, 1792.
M. Antonietti, J. Conrad, A. Thünemann, Macromolecules 1994, 27, 6007;
M. R. J. Vos, G. E. Jardl, A. L. Pallas, M. Breurken, O. L. J. van Asselen, P. H. H. Bomans, Ph. E. L. G. Leclère, P. M. Frederik, R. J. M. Nolte, N. A. J. M. Sommerdijk, J. Am. Chem. Soc. 2005, 127, 16768.
See for example: (a) S. Tamaru, M. Takeuki, M. Sano, S. Shinkai, Angew. Chem. 2002, 114, 881.
(b) G. Mieden-Gundert, L. Klein, M. Fischer, F. Vögtle, K. Heuzé, J. L. Pozzo, M. Vallier, F. Fages, Angew. Chem. 2001, 113, 3266.
(c) U. Maitra, S. Mukhopadhyay, A. Sarkar, P. Rao, S. S. Indi, Angew. Chem. 2001, 113, 2341.
(d) F. S. Schoonbeek, J. H. van Esch, R. Hulst, R. M. Kellog, B. L. Feringa, Chem-Eur. J. 2000, 6, 2633.
(e) R. Wang, C. Geiger, L. Chen, B. Swanson, D. G. Whitten, J. Am. Chem. Soc. 2000, 122, 2399.
(f) J. H. van Esch, B. L. Feringa, Angew. Chem. 2000, 112, 2351.
(g) P. Terech, R. G. Weiss, Chem. Rev. 1997, 97, 3133.
(a) A. Ajayaghosh, S. J. George, V. K. Praveen, Angew. Chem., Int. Ed. 2003, 42, 332.
(b) W. Y. Huang, S. Matsuoka, T. K. Kwei, Y. Okamoto, Macromolecules 2001, 34, 7166.
(c) C. Geiger, M. Stanescu, L. Chen, D. G. Whitten, Langmuir 1999, 15, 2241.
(d) M. Grell, D. D. C. Bradley, X. Long, T. Chamberlain, M. Inbasekaran, E. P. Woo, M. Soliman, Acta Polym. 1998, 49, 439.
(e) T. Brotin, R. Utermöhlen, F. Fages, H. Boucas-Laurent, J. P. Desvergne, J. Chem. Soc, Chem. Commun. 1991, 416.
(f) T. M. Swager, C. J. Gil, M. S. Wrighton, J. Phys. Chem. 1995, 99, 4886.
(g) A. Ajayaghosh, R. Varghese, S. J. George, C. Vijayakumar, Angew. Chem., Int. Ed. 2006, 45, 1141.
(h) K. Sugiyasu, N. Fujita, S. Shinkai, Angew. Chem., Int. Ed. 2004, 43, 1229.
(i) A. Ajayaghosh, R. Varghese, V. K. Praveen, S. Mahesh, Angew. Chem, Int. Ed. 2006, 45, 3261.
(a) D. B. A. Rep, R. Roelfsema, J. H. van Esch, F. S. Schoonbeek, R. M. Kellogg, B. L. Feringa, T. T. M. Palstra, T. M. Klapwijk, Adv. Mater. 2000, 12, 563.
(b) F. S. Schoonbeek, J. H. van Esch, B. Wegewijs, D. B. A. Rep, M. P. de Haas, T. M. Klapwijk, R. M. Kellog, B. L. Feringa, Angew. Chem., Int. Ed. 1999, 38, 1393.
See for example: (a) M. L. Bushey, A. Hwang, P. W. Stephens, C. Nickholls, Angew. Chem., Int. Ed. 2002, 41, 2828.
(b) M. P. Lightfoot, F. S. Mair, R. C. Pritchard, J. E. Warren, Chem. Commun. 1999, 1945.
(c) V. Percec, C.-H. Ahn, T. K. Bera, G. Ungar, D. J. P. Yeardley, Chem.-Eur. J. 1999, 5, 1070.
See for example: (a) W. Shu, S. Valiyaveetil, Chem. Commun. 2002, 1350.
(b) J. J. van Gorp, J. A. J. M. Vekemans, E. W. Meijer, J. Am. Chem. Soc. 2002, 124, 14759.
(c) L. Brunsveld, H. Zhang, M. Glasbeek, J. A. J. M. Vekemans, E. W. Meijer, J. Am. Chem. Soc. 2000, 722, 6175.
(d) A. R. A. Palmans, J. A. J. M. Vekemans, E. E. Havinga, E. W. Meijer, Angew. Chem., Int. Ed. Engl. 1997, 36, 2648.
(e) R. Kleppinger, P. Lillya, C. Yang, J. Am. Chem. Soc. 1997, 119, 4097.
For a review see: (a) G. G. Wallace, L. A. P. Kane-Maguire, Adv. Mater. 2002, 14, 953.
(b) S. B. Adeloju, G. G. Wallace, Analyst 1996, 121, 699.
(c) W. Schuhmann, Mikrochim. Acta 1995, 121, 1.
(d) P. N. Bartlett, P. R. Birkin, Synth. Met. 1993, 61, 15.
(e) For a review about bioelectronics see: I. Willner, E. Katz, Angew. Chem., Int. Ed. 2000, 39, 1180.
(a) B. S. Gaylord, A. J. Heeger, G. C. Bazan, J. Am. Chem. Soc. 2003, 125, 896.
(b) K. P. R. Nilsson, O. Inganäs, Nat. Mater. 2003, 2, 419.
(c) H.-A. Ho, M. Boissinot, M. G. Bergeron, G. Corbeil, K. Doré, D. Boudreau, M. Leclerc, .J. Am. Chem. Soc. 2003, 125, 896.
(d) S. Bernier, S. Garreau, M. Béra-Abérem, C. Gravel, M. Leclerc, J. Am. Chem. Soc. 2002, 124, 12463.
(e) P. C. Ewbank, G. Nuding, H. Suenaga, R. D. McCullough, S. Shinkai, Tetrahedron Lett. 2001, 42, 155.
(f) L. Chen, D. W. McBranch, H.-L. Wang, R. Helgeson, F. Wudl, D. Whitten, Proc. Natl. Acad. Sci. U.S.A. 1999, 96, 12287.
A. Yassar, G. Horowitz, P. Valat, V. Wintgens, M. Hmyene, F. Deloffre, P. Srivastava, P. Lang, F. Garnier, J. Phys. Chem. 1995, 99, 9155.
M. Sundberg, O. Inganäs, S. Stafström, G. Gustafsson, B. Sjögren, Solid State Commun. 1989, 71, 435.
Ph. Leclère, M. Surin, O. Henze, P. Jonkheijm, F. Biscarini, M. Cavallini, W. J. Feast, A. F. M. Kilbinger, R. Lazzaroni, E. W. Meijer, A. P. H. J. Schenning, J. Mater. Chem. 2004, 16, 4452.
Ribbon-like fibrils are formed when 2 is deposited on silicon wafers or graphite. However, the present rod-like assemblies of 1 appear considerably more rigid and are more homogeneous in shape.
A similar value (381 nm) was obtained for 2 in the same solvent.
The shape and dimensions of the aggregates in solution were confirmed by preliminary SAXS and DLS experiments.
(a) S. Hotta, K. Waragai, Adv. Mater. 1993, 5, 896.
(b) D. Fichou, J. Mater. Chem. 2000, 10, 571.
J. Cornil, D. Beljonne, J.-P. Calbert, J.-L. Brédas, Adv. Mater. 2001, 13, 1053.
C. Quattrocchi, R. Lazzaroni, J. L. Brédas, Chem., Phys. Lett. 1993, 208, 120.
The complex was formed in the presence of 2% v/v DMSO in water. It was therefore impossible to detect any low wavelength CD signal relative to the polypeptidic chain.
(a) D. Zanuy, C. Alemán, S. Muñoz-Guerra, Biopolymers 2002, 63, 151.
(b) E. A. Ponomarenko, A. J. Waddon, D. A. Tirrell, W. J. Macknight, Langmuir 1996, 12, 2169.
(c) M. Tabet, V. Labroo, P. Sheppard, T. Sasaki, J. Am. Chem. Soc. 1993, 115, 3866.
The low intensity of the CD effect is attributed to the large distance between the oligothiophene segment and the chiral centers of the PLG, see e.g. D. B. Amabilino, E. Ramos, J.-L. Serrano, T. Sierra, J. Veciana, J. Am. Chem. Soc. 1998, 120, 9126.
D. Zanuy, C. Alemán, Biopolymers 1999, 49, 497.
(a) E. Yashima, H. Goto, Y. Okamoto, Macromolecules 1999, 32, 7942.
(b) B. M. W. Langeveld-Voss, D. Beljonne, Z. Shuai, R. A. J. Janssen, S. C. J. Meskers, E. W. Meijer, J.-L. Brédas, Adv. Mater. 1998, 10, 1343.
P. S. Heeger, A. J. Heeger, Proc. Natl. Acad. Sci U.S.A. 1999, 96, 12219.
(a) J. Wang, D. Wang, E. K. Miller, D. Moses, G. C. Bazan, A. J. Heeger, Macromolecules 2000, 33, 5153.
(b) D. Wang, X. Gong, P. S. Heeger, F. Rininsland, G. C. Bazan, A. J. Heeger, Proc. Natl. Acad. Sci. U.S.A. 2002, 99, 49.
P. Samorì, V. Francke, T. Mangel, K. Müllen, J. Rabe, Opt. Mater. 1998, 9, 390.
S. L. Mayo, B. D. Olafson, W. A. Goddard, III, J. Phys. Chem. 1990, 94, 8897.
A. Gesquière, M. M. S. Abdel-Mottaleb, S. De Feyter, F. C. De Schryver, F. Schoonbeek, J. van Esch, R. M. Kellogg, B. L. Feringa, A. Calderone, R. Lazzaroni, J. L. Brédas, Langmuir 2000, 16, 10385.
M. C. Zerner, G. H. Loew, R. F. Kirchner, U. T. Mueller-Westerhoff, J. Am, Chem., Soc. 1980, 102, 589.
S. Kotani, K. Shiina, K. Sonogashira, J. Organomet. Chem. 1992, 429, 403.
