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  • Publication
    Accès libre
    Macrocyclic Effects in the Mesomorphic Properties of Liquid-Crystalline Pillar[5]- and Pillar[6]arenes
    Nierengarten, Iwona
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    Holler, Michel
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    Karmazin-Brelot, Lydia
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    Barberá, Joaquín
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    Nierengarten, Jean-François
    Whereas the reaction of 1,4-bis(2-bromoethyloxy)benzene (4) with paraformaldehyde in the presence of BF3·Et2O afforded exclusively the cyclopentameric pillar[5]arene derivative (5), both cyclopenta- and cyclohexameric macrocycles 5 and 6 were obtained when the reaction of 4 with paraformaldehyde was performed at 45 °C in CHCl3 with FeCl3 as the catalyst. Treatment of compounds 4–6 with sodium azide provided the corresponding polyazides, to which a cyanobiphenyl building block was subsequently grafted to generate model compound 1, pillar[5]arene 2, and pillar[6]arene 3, bearing two, ten and twelve mesomorphic subunits, respectively. The liquid-crystalline and thermal properties of the compounds were investigated by polarized optical microscopy (POM), differential scanning calorimetry (DSC), and X-ray diffraction (XRD). Comparison of the liquid-crystalline properties of macrocycles 2 and 3 with those of 1 revealed the strong influence of the macrocyclic pillar[n]arene core on the mesomorphic properties. Whereas only a monotropic mesophase was observed for 1, a broad enantiotropic mesophase was evidenced for both pillar[n]arene derivatives.
  • Publication
    Accès libre
    Piling Up Pillar[5]arenes To Self-Assemble Nanotubes
    Nierengarten, Iwona
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    Ben Aziza, Haifa
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    Holler, Michel
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    Abidi, Rym
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    Barberá, Joaquín
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    ;
    Nierengarten, Jean-François
    New liquid-crystalline pillar[5]arene derivatives have been prepared by grafting first- generation Percec-type poly(benzylether) dendrons onto the macrocyclic scaffold. The molecules adopt a disc-shaped structure perfectly suited for self-organization into a columnar liquid-crystalline phase. In this way, the pillar[5]arene cores are piled up, thus forming a nanotubular wire encased within a shell of peripheral dendrons. The capability of pillar[5]arenes to form inclusion complexes has been also exploited. Specifically, detailed binding studies have been carried out in solution with 1,6- dicyanohexane as the guest. Inclusion complexes have also been prepared in the solid state. Supramolecular organization into the Colh mesophase has been deduced from X-ray diffraction data and found to be similar to that observed within the crystal lattice of a model inclusion complex prepared from 1,4-dimethoxypillar[5]arene and 1,6- dicyanohexane.
  • Publication
    Accès libre
    Building liquid crystals from the 5-fold symmetrical pillar[5]arene core
    Nierengarten, Iwona
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    ;
    Holler, Michel
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    Nierengarten, Jean-Francois
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    Comparison of the liquid-crystalline properties of a pillar[5]arene core functionalized with 10 mesogenic cyanobiphenyl units with those of a corresponding model compound revealed the strong influence of the macrocyclic pillar[5]arene core on the mesomorphic properties.