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Chem. Mater. 2005, 17, 6430-6435
Single Crystalline Submicrotubes from Small Organic Molecules Yong Sheng Zhao,†,‡ Wensheng Yang,†,§ Debao Xiao,† Xiaohai Sheng,† Xia Yang,| Zhigang Shuai,| Yi Luo,⊥ and Jiannian Yao*,† Key Laboratory of Photochemistry, Center for Molecular Science, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, China, College of Chemistry, Jilin UniVersity, Changchun 130023, China, Key Laboratory of Organic Solid, Center for Molecular Science, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, China, Theoretical Chemistry, Royal Institute of Technology, SCFAB, S-106 91 Stockholm, Sweden, and Graduate School, Chinese Academy of Sciences, Beijing 100039, China ReceiVed August 29, 2005. ReVised Manuscript ReceiVed October 20, 2005
The single crystalline submicrotubes of a small organic functional molecule, 2,4,5-triphenylimidazole (TPI), were successfully prepared with a facile method. A series of characterizations indicated that the tubes were obtained from the rolling followed by seaming of a preorganized two-dimensional sheet-like structure, whose formation was due to the efficient cooperation of several molecular recognition elements. The length and diameter of the TPI tubes can be readily controlled by adjusting the experimental conditions. The as-prepared submicrotubes have intensive luminescence and size-dependent optical properties, which allows them to find potential applications in novel optical and optoelectronic devices together with their single crystalline structure and good stability. The strategy described here should give a useful enlightenment for the design and fabrication of tubular structures from small organic molecules.
* Correspondening author. E-mail:
[email protected]. † Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences. ‡ Graduate School, Chinese Academy of Sciences. § Jilin University. | Key Laboratory of Organic Solids, Institite of Chemistry, Chinese Academy of Sciences. ⊥ Royal Institute of Technology.
are of the noncovalent types, such as hydrogen bond (Hbond), π-π interaction, van der Waals contact, and charge transfer (CT) interaction. Owing to their diversity, tailorability, and multifunctionality, it is of great significance to extend the relative researches to small organic molecules. So far, most of organic nano- and submicrotubes are fabricated from the self-stacking of disk-like molecules7,13,14 and the self-assembly of multifunctional molecules such as dendrimers15 and amphiphiles.16 Template method17,18 has been applied to prepare organic nanotubes but most of the products have amorphous structures. Extensive studies on inorganic nanotubes19-21 suggest that a more readily way to prepare tubules is through the rolling of lamellar structures. It has been proposed that there also exists the possibility to acquire organic nanotubes by the rolling mechanism.22,23 There have been some reports on the construction of twodimensional (2D) lamellar supramolecular structures via molecular recognition elements such as hydrogen bond (Hbond), π-π interaction, van der Waals contact, etc. from organic molecules.24,25 However, to the best of our knowl-
(1) Xia, Y.; Yang, P.; Sun, Y.; Wu, Y., Mayers, B.; Gates, B.; Yin, Y.; Kim, F.; Yan, H. AdV. Mater. 2003, 15, 353. (2) Hu, J.; Ouyang. M.; Yang, P.; Lieber, C. M. Nature 1999, 399, 48. (3) Che, G.; Lakshmi, B. B.; Fisher, E. R.; Martin, C. R. Nature 1998, 393, 346. (4) Collins, P. G.; Zettl, A.; Bando, H.; Thess, A.; Smalley, R. E. Science 1997, 278, 100. (5) Star, A.; Lu, Y.; Bradley, K.; Gruner, G. Nano Lett. 2004, 4, 1587. (6) Parthasarathy, R. V.; Martin, C. R. Nature 1994, 369, 298. (7) Ghadiri, M. R.; Granja, J. R.; Milligan, R. A., McRee, D. E., Khazanovich, N. Nature 1993, 366, 324. (8) Yan, D.; Zhou, Y.; Hou, J. Science 2004, 303, 65. (9) Fu, H. B.; Yao, J. N. J. Am. Chem. Soc. 2001, 123, 1434. (10) Fu, H. B.; Loo, B. H.; Xiao, D. B.; Xie, R. M.; Ji, X. H.; Yao, J. N.; Zhang, B. W.; Zhang, L. Q. Angew. Chem., Int. Ed. 2002, 41, 962. (11) Xiao, D. B.; Xi, L.; Yang, W. S.; Fu, H. B.; Shuai, Z. G.; Fang, Y.; Yao, J. N.; J. Am. Chem. Soc. 2003, 125, 6740. (12) Tian, Z. Y.; Chen, Y.; Yang, W. S.; Yao, J. N.; Zhu, L. Y.; Shuai, Z. G. Angew. Chem. Int. Ed. 2004, 43, 4060.
(13) Bong, D. T.; Clark, T. D.; Granja, J. R.; Ghadiri, M. R. Angew. Chem., Int. Ed. 2001, 40, 988. (14) Hong, B. H.; Lee, J. Y.; Lee, C. W.; Kim, J. C.; Bae, S. C.; Kim, K. S. J. Am. Chem. Soc. 2001, 123, 10748. (15) Yamaguchi, T.; Ishii, N.; Tashiro, K.; Aida, T. J. Am. Chem. Soc. 2003, 125, 13934. (16) John, G.; Masuda, M.; Okada, Y.; Yase, K.; Shimizu, T. AdV. Mater. 2001, 13, 715. (17) Martin, C. R. Science 1994, 266, 1961. (18) Zhao, L. Y.; Yang, W. S.; Ma, Y.; Yao, J. N.; Li, Y. L.; Liu, H. B. Chem. Commun. 2003, 2442. (19) Iijima, S. Nature 1991, 354, 56. (20) Schaak, R. E.; Mallouk, T. E. Chem. Mater. 2000, 12, 3427. (21) Li, Y. D.; Li, X. L.; He, R. R.; Zhu, J.; Deng, Z. X. J. Am. Chem. Soc. 2002, 124, 1411. (22) Hartgerink, J. D.; Clark. T. D.; Ghadiri, M. R. Chem. Eur. J. 1998, 4, 1367. (23) Langley, P. J.; Hulliger, J. Chem. Soc. ReV. 1999, 28, 279.
Introduction During the past decades, one-dimensional nano- and submicrostructures, especially tubular ones, have attracted extensive investigation due to their unique optical and electronic properties1 and their potential applications in various fields such as optoelectronics, catalysis, energy storage, and so on.2-5 However, most of the present works were focused on inorganics and macromolecules6-8 whereas less attention has been paid to tubes from low-molecularweight organic compounds although it is well-known that the electronic and optical properties of organic lowdimensional materials are fundamentally different from those of inorganic ones,9-12 because the intermolecular interactions
10.1021/cm051949t CCC: $30.25 © 2005 American Chemical Society Published on Web 11/15/2005
Single Crystalline Submicrotubes Scheme 1. Chemical Structure (a) and Optimized Geometry (b) of Single 2,4,5-Triphenylimidazole (TPI) Molecule
edge, the construction of organic tubes via the rolling of lamellar structures has hardly been described in practice. Herein, for the first time, we describe the fabrication of a single crystalline submicrotube from a small organic functional molecule, 2,4,5-triphenylimidazole (TPI) (Scheme 1), via the rolling and seaming of a 2D lamellar structure, directed by the cooperation of several noncovalent interactions. The length and diameter of the as-fabricated TPI tubes can be readily controlled by adjusting the experimental conditions such as temperature and sonication time. The submicrotubes have intensive luminescence, size-dependent optical properties, and good stability, which allow them to find potential applications in novel optical and optoelectronic devices. The strategy described here should give a useful enlightenment for the design and fabrication of tubular structures from small organic molecules. Experimental Section Materials. The model compound used in our work, 2,4,5triphenylimidazole (Scheme 1), was purchased from Sigma-Aldrich and used without further treatment. Ultrapure water with a resistivity of 18.2 MΩ‚cm, which acts as the poor solvent, was produced using a Milli-Q apparatus (Millipore, America) and was filtered using inorganic membrane with a pore size of 0.02 µm (Whatman International Ltd) just before use. Procedure. The TPI submicrotubes were prepared through a facile reprecipitation method. In a typical preparation, 400 µL of TPI stock solution in good solvent such as ethanol or acetone (10-3 M) was injected rapidly (
