Abstract
The advent of supramolecular chemistry in the last decades of the 20 th century has provided chemists with a wealth of new possibilities to synthesize molecular structures and materials that are held together by relatively weak, non-covalent interactions, such as hydrogen bonding, coordinative interactions, electrostatic and van der Waals interactions. 1 The creation of even more complex supramolecular architectures has recently become possible by applying the concept of hierarchical self-assembly, i.e., the non-covalent organization of molecules and macromolecules which takes places over distinct multiple levels, in which the assembly processes gradually decrease in strength. The hierarchical structure of supramolecular assemblies leads to a parallel hierarchy of dynamic processes. Following these principles, the goal of this work is to gain unprecedented control over the structure, self-organization and molecular dynamics of soft-matter systems by exploiting a combination of classical macromolecular architectures and specific supramolecular interactions. This will enable the building of macromolecular assemblies with adaptive structure and stimuli-responsive properties. Our original strategy is to tune the self-assembly of block copolymers via metal-ligand interactions. Firstly, block copolymers bearing a ligand at the chain end will be synthesized. Secondly, systems presenting a hierarchy in both dynamics and structure will be obtained by relying on the interplay between the self-assembling ability of copolymers into micelles and the formation of metal-ligand complexes. Thirdly, the dynamic properties of these structures will be analyzed in solution by rheology.