Hierarchical superstructures by combining crystallization-driven and molecular self-assembly.

Combining the unique corona structure of worm-like patchy micelles immobilized on a polymer fibre with the molecular self-assembly of 1,3,5-benzenetricarboxamides (BTAs) leads to hierarchical superstructures with a fir tree-like morphology. For this purpose, worm-like patchy micelles bearing pendant, functional tertiary amino groups in one of the corona patches were prepared by crystallization-driven self-assembly and immobilized on a supporting polystyrene fibre by coaxial electrospinning. The obtained patchy fibres were then immersed in an aqueous solution of a tertiary amino-functionalized BTA to induce patch-mediated molecular self-assembly to well-defined fir-tree like superstructures upon solvent evaporation. Interestingly, defined superstructures are obtained only if the pendant functional groups in the surface patches match with the peripheral substituents of the BTA, which is attributed to a local increase in BTA concentration at the polymer fibres' surface.