Swallow-Tail Substituted Liquid Crystalline Perylene Bisimides: Synthesis and Thermotropic Properties.

Tailor-made synthesis and structure-property relationship of several swallow-tail N-substituted perylene bisimide (PBI) dyes are presented. PBI derivatives were synthesized by two distinct synthetic approaches, the details being evaluated herein. All the PBIs carry either alkyl swallow-tail or oligo...

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Publicado en:Journal of the American Chemical Society Vol. 131; no. 40; pp. 14442 - 14454
Autores principales: Wicklein, André, Lang, Andreas, Muth, Mathis, Thelakkat, Mukundan
Formato: Artículo
Publicado: American Chemical Society 10/14/2009
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Acceso en línea:Ver este registro en EBSCOhost
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      dt: 10/14/2009
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      pub: American Chemical Society
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        10.1021/ja905260c
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        atl: Swallow-Tail Substituted Liquid Crystalline Perylene Bisimides: Synthesis and Thermotropic Properties.
      aug:
        au:
          Wicklein, André
          Lang, Andreas
          Muth, Mathis
          Thelakkat, Mukundan
        affil: Department of Macromolecular Chemistry I, Applied Functional Polymers, Universität Bayreuth, Universitatsstraße 30, 95440 Bayreuth, Germany
      su:
        Perylene
        Thermotropism
        Microscopy
        Optical diffraction
        Crystallization
      sug:
        subj:
          Perylene
          Thermotropism
          Microscopy
          Optical diffraction
          Crystallization
      ab: Tailor-made synthesis and structure-property relationship of several swallow-tail N-substituted perylene bisimide (PBI) dyes are presented. PBI derivatives were synthesized by two distinct synthetic approaches, the details being evaluated herein. All the PBIs carry either alkyl swallow-tail or oligoethyl-englycolether (OEG) swallow-tail moieties as N-substituents, and many of them are unsymmetrically substituted. We avoided substitution at bay positions of the perylene core to maintain the planarity and strong r-v interactions, which favor intermolecular order and charge carrier transport. The thermotropic behavior, which is strongly influenced by the nature of the substituents was investigated using differential scanning calorimetry (DSC), polarization optical microscopy (POM), and X-ray diffraction measurements (XRD). The introduction of OEG swallow-tail units facilitates thermotropic liquid crystalline behavior in most cases and the unsymmetrical substitution allowed the tuning of the mesophase-width. The mesophases exhibit characteristic columnar hexagonal (Col) packing arising from π-π interactions between cofacially orientated perylene molecules. Thus, the inherent tendency of PBI molecules for crystallization could be effectively suppressed by incorporating flexible OEG swallow-tail units only at imide positions. This molecular design was crucial to obtain liquid crystallinity and intracolumnar long-range order. The substituents did not influence the electronic energy levels such as HOMO and LUMO.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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