Chain Architecture Dependent 3‐Dimensional Supramolecular Assembly of Rod‐Coil Molecules with a Conjugated Hexa‐p‐phenylene Rod

Abstract

AbstractSummary: We have prepared hexa‐p‐phenylene based rod‐coil molecules with identical coil volume fractions, but different poly(propylene oxide) (PPO) coil architectures (linear versus dibranched), and investigated their self‐assembling behavior in the solid state by small angle X‐ray scattering (SAXS) and transmission electron microscopy (TEM) techniques. Rod‐coil molecules with a linear PPO coil showed a honeycomb‐like lamellar assembly of rod segments with hexagonally arrayed PPO coil perforations. In contrast, the rod‐coil molecules with dibranched PPO coils self‐organized into rod bundles with a body centered tetragonal symmetry surrounded by a PPO coil matrix. These results demonstrate that the steric hindrance at the rod/coil interface arising from coil architectural variation is a dominant parameter governing supramolecular rod assembly in the rod‐coil system.TEM images and schematic illustrations of the self‐assembled structures of rod‐coil molecules with linear (left) and dibranched (right) PPO coils, respectively.imageTEM images and schematic illustrations of the self‐assembled structures of rod‐coil molecules with linear (left) and dibranched (right) PPO coils, respectively.