Stimulus-Responsive Azobenzene Supramolecules: Fibers, Gels, and Hollow Spheres

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• 作者：Sumi Lee ; Seungwhan Oh ; Joosub Lee ; Yashwardhan Malpani ; Young-Sik Jung ; Baotao Kang ; Jin Yong Lee ; Kazunari Ozasa ; Takashi Isoshima ; Sang Yun Lee ; Masahiko Hara ; Daisuke Hashizume ; Jong-Man Kim
• 刊名：Langmuir
• 出版年：2013
• 出版时间：May 14, 2013
• 年：2013
• 卷：29
• 期：19
• 页码：5869-5877
• 全文大小：559K
• 年卷期：v.29,no.19(May 14, 2013)
• ISSN：1520-5827

文摘

Novel, stimulus-responsive supramolecular structures in the form of fibers, gels, and spheres, derived from an azobenzene-containing benzenetricarboxamide derivative, are described. Self-assembly of tris(4-((E)-phenyldiazenyl)phenyl)benzene-1,3,5-tricarboxamide (Azo-1) in aqueous organic solvent systems results in solvent dependent generation of microfibers (aq DMSO), gels (aq DMF), and hollow spheres (aq THF). The results of a single crystal X-ray diffraction analysis of Azo-1 (crystallized from a mixture of DMSO and H₂O) reveal that it possesses supramolecular columnar packing along the b axis. Data obtained from FTIR analysis and density functional theory (DFT) calculation suggest that multiple hydrogen bonding modes exist in the Azo-1 fibers. UV irradiation of the microfibers, formed in aq DMSO, causes complete melting while regeneration of new fibers occurs upon visible light irradiation. In addition to this photoinduced and reversible phase transition, the Azo-1 supramolecules display a reversible, fiber-to-sphere morphological transition upon exposure to pure DMSO or aq THF. The role played by amide hydrogen bonds in the morphological changes occurring in Azo-1 is demonstrated by the behavior of the analogous, ester-containing tris(4-((E)-phenyldiazenyl)phenyl)benzene-1,3,5-tricarboxylate (Azo-2) and by the hydrogen abstraction in the presence of fluoride anions.