Macroscopically Aligned Ionic Self‐Assembled Perylene‐Surfactant Complexes within a Polymer Matrix

Ionic self‐assembled (ISA) surfactant complexes present a facile concept for self‐assembly of various functional materials. However, no general scheme has been shown to allow their overall alignment beyond local polydomain‐like order. Here we demonstrate that ionic complexes forming a columnar liquid‐crystalline phase in bulk can be aligned within polymer blends upon shearing, taken that the matrix polymers have sufficiently high molecular weight. We use an ISA complex of N , N ′‐bis(ethylenetrimethylammonium)perylenediimide/bis(2‐ethylhexyl) phosphate (Pery‐BEHP) blended with different molecular weight polystyrenes (PS). Based on X‐ray scattering studies and transmission electron microscopy the pure Pery‐BEHP complex was found to form a two‐dimensional oblique columnar phase where the perylene units stack within the columns. Blending the complex with PS lead to high aspect ratio Pery‐BEHP aggregates with lateral dimension in the mesoscale, having internal columnar liquid‐crystalline order similar to the pure Pery‐BEHP complex. When the Pery‐BEHP/PS blend was subjected to a shear flow field, the alignment of perylenes can be achieved but requires sufficiently high molecular weight of the polystyrene matrix. The concept also suggests a simple route for macroscopically aligned nanocomposites with conjugated columnar liquid‐crystalline functional additives.