Columnar Mesophase Formation of Cyclohexa‐<i>m</i>‐phenylene‐Based Macrocycles

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公開日
2006-12-27
権利情報
  • http://onlinelibrary.wiley.com/termsAndConditions#vor
DOI
  • 10.1002/asia.200600338
公開者
Wiley

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説明

<jats:title>Abstract</jats:title><jats:p>Two novel discotic macrocycles, substituted cyclohexa‐<jats:italic>m</jats:italic>‐phenylene (CHP) and cyclo‐3,6‐trisphenanthrylene (CTP), and the linear oligomer 3,3′:6′,3′′‐terphenanthrene (TP) as a model substance have been synthesized by repetitive cross‐coupling reactions. To correlate the molecular design with the supramolecular architecture and the established macroscopic order, 2D wide‐angle X‐ray scattering experiments were performed on mechanically extruded filaments. At room temperature in their crystalline phases, all three compounds revealed columnar assemblies in which the macrocycles self‐organized by π‐stacking interactions. The degree of macroscopic order was found to depend upon the planarity and stiffness of the aromatic core. The flexible CHP ring showed a poor macroscopic order of the columnar structures and a low isotropization temperature, whereas the more‐planar, less‐flexible CTP self‐assembled into well‐defined superstructures. The larger π‐stacking area and the more‐pronounced intermolecular interactions for CTP led to the formation of a mesophase over a very large temperature range. The surprising columnar organization of the “open” TP system was explained by back‐folding of the molecule into a ringlike structure.</jats:p>

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