Supramolecularly Engineered Perylene Bisimide Assemblies Exhibiting Thermal Transition from Columnar to Multilamellar Structures.

Perylene 3,4:9,10-tetracarboxylic acid bisimide (PBI) was functionalized with ditopic cyanuric acid to organize it into complex columnar architectures through the formation of hydrogen-bonded supermacrocycles (rosette) by complexing with ditopic melamines possessing solubilizing alkoxyphenyl substit...

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Publicado en:Journal of the American Chemical Society Vol. 134; no. 18; pp. 7983 - 7995
Autores principales: Yagai, Shiki, Usui, Mari, Seki, Tomohiro, Murayama, Haruno, Kikkawa, Yoshihiro, Uemura, Shinobu, Karatsu, Takashi, Kitamura, Akihide, Asano, Atsushi, Seki, Shu
Formato: Artículo
Publicado: American Chemical Society 5/9/2012
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Acceso en línea:Ver este registro en EBSCOhost
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      pub: American Chemical Society
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        10.1021/ja302574b
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        atl: Supramolecularly Engineered Perylene Bisimide Assemblies Exhibiting Thermal Transition from Columnar to Multilamellar Structures.
      aug:
        au:
          Yagai, Shiki
          Usui, Mari
          Seki, Tomohiro
          Murayama, Haruno
          Kikkawa, Yoshihiro
          Uemura, Shinobu
          Karatsu, Takashi
          Kitamura, Akihide
          Asano, Atsushi
          Seki, Shu
        affil:
          Department of Applied Chemistry & Biochemistry, Graduate School of Engineering, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
          CREST, Japan Science and Technology Agency (JST), 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
          Office of Society-Academia Collaboration for Innovation, Kyoto University, Yoshida-Honmachi, Sakyo-ku, Kyoto 606-8501, Japan
          National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki 305-8562, Japan
          Department of Applied Chemistry & Biochemistry, Graduate School of Science and Technology, Kumamoto University, Kurokami 2-39-1, Kumamoto 860-8555, Japan
          Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1, Yamadaoka, Suita, Osaka 565-0871, Japan
      su:
        Clustering of particles
        Supramolecular chemistry
        Bisimides
        Perylene
        Spectrum analysis
        Hydrogen bonding
        Pi bonds (Chemistry)
      sug:
        subj:
          Clustering of particles
          Supramolecular chemistry
          Bisimides
          Perylene
          Spectrum analysis
          Hydrogen bonding
          Pi bonds (Chemistry)
      ab: Perylene 3,4:9,10-tetracarboxylic acid bisimide (PBI) was functionalized with ditopic cyanuric acid to organize it into complex columnar architectures through the formation of hydrogen-bonded supermacrocycles (rosette) by complexing with ditopic melamines possessing solubilizing alkoxyphenyl substituents. The aggregation study in solution using UV-vis and NMR spectroscopies showed the formation of extended aggregates through hydrogen-bonding and π-π stacking interactions. The cylindrical fibrillar nanostructures were visualized by microscopic techniques (AFM, TEM), and the formation of lyotropic mesophase was confirmed by polarized optical microscopy and SEM. X-ray diffraction study revealed that a well-defined hexagonal columnar (Col) structure was formed by solution-casting of fibrillar assemblies. All of these results are consistent with the formation of hydrogen-bonded PBI rosettes that spontaneously organize into the Col structure. Upon heating the Col structure in the bulk state, a structural transition to a highly ordered lamellar (Lam) structure was observed by variable-temperature X-ray diffraction, differential scanning calorimetry, and AFM studies. IR study showed that the rearrangement of the hydrogen-bonding motifs occurs during the structural transition. These results suggest that such a striking structural transition is aided by the reorganization in the lowest level of self-organization, i.e., the rearrangement of hydrogen-bonded motifs from rosette to linear tape. A remarkable increase in the transient photoconductivity was observed by the flash-photolysis time-resolved microwave conductivity (FP-TRMC) measurements upon converting the Col structure to the Lam structure. Transient absorption spectroscopy revealed that electron transfer from electron-donating alkoxyphenyl groups of melamine components to electron-deficient PBI moieties takes place, resulting in a higher probability of charge carrier generation in the Lam structure compared to the Col structure.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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