Microfibres and macroscopic films from the coordination-driven hierarchical self-assembly of cylindrical micelles

Anisotropic nanoparticles prepared from block copolymers are of growing importance as building blocks for the creation of synthetic hierarchical materials. However, the assembly of these structural units is generally limited to the use of amphiphilic interactions. Here we report a simple, reversible coordination-driven hierarchical self-assembly strategy for the preparation of micron-scale fibres and macroscopic films based on monodisperse cylindrical block copolymer micelles. Coordination of Pd(0) metal centres to phosphine ligands immobilized within the soluble coronas of block copolymer micelles is found to induce intermicelle crosslinking, affording stable linear fibres comprised of micelle subunits in a staggered arrangement. The mean length of the fibres can be varied by altering the micelle concentration, reaction stoichiometry or aspect ratio of the micelle building blocks. Furthermore, the fibres aggregate on drying to form robust, self-supporting macroscopic micelle-based thin films with useful mechanical properties that are analogous to crosslinked polymer networks, but on a longer length scale.