Materials with tunable properties from metallo-supramolecular block copolymers

(eng) This thesis deals with new materials from metallo-supramolecular block copolymers containing a stimuli responsive junction based on metal-terpyridine complex. The hierarchical self-assembly of the diblock copolymer based on polystyrene-block-poly(tert-butylacrylate) end-functionalized with a terpyridine (PS-b-PtBA-[) was investigated. Micelles were prepared from the synthesized block copolymers in a selective solvent of the PtBA block as the first level of self-assembly. Several strategies were investigated in dilute regime to tune the morphology of those micelles. The second level of self-assembly was triggered upon addition of metal ions in concentrated micellar solution, leading to a micellar gel whose strength depends on the added metal ion. Furthermore, we have shown that the metal-terpyridine complexes connecting micelles are reversibly broken under a mechanical stimulus, evidencing the self-healing properties of the synthesized materials. In the following, the PS-[Co]-PEO and PS-[Ni]-PEO metallo-supramolecular block copolymers containing a stimuli responsive junction were synthesized, and their self-assembly was investigated in solution as well as in bulk. In the latter case, we were interested in the cylindrical morphology of the PEO minor block, oriented normal to the surface of the film. Indeed, the cleavage of the complex located at the junction between the two blocks, followed by the removal of the minor block will lead to nanoporous thin films bearing terpyridine moieties at the pore walls.