Supramolecular interactions for controlling the structure, self-organization and dynamics of stimuli-responsive polymeric systems

In the last years, the advent of supramolecular chemistry has provided chemists with new possibilities to synthesize complex structures and dynamic materials by self-assembly. By virtue of their properties, metal–ligand interactions are particularly promising for the synthesis of supramolecular polymers and the construction of “smart” materials with self-restructuring abilities. Among them, supramolecular gels constitute a very interesting sub-class because of numerous applications in various fields. In this frame, the goal of this thesis is to gain an unprecedented control over the structure, self-organization and molecular dynamics of polymeric gels by exploiting a novel combination of classical macromolecular architectures and supramolecular interactions of the metal–ligand type. The first goal of this thesis relies on the synthesis of well-defined copolymers, functionalized with a ligand of interest. These building blocks will then be used in the design of supramolecular materials with responsive properties. Precisely, the coordination of metal to ligands will be used to link micellar objects, obtained by the self-assembly of covalent block copolymers. The rheological behaviour of the accordingly obtained materials will be thoroughly characterized in order to establish relationships between their structure, dynamics and mechanical properties. The present thesis aims at studying in details the response of these systems to external stimuli. These stimuli-responsive properties will be inherent to the supramolecular materials and further obtained by using stimuli-responsive polymer sequences as building blocks.