Templated synthesis of Supramolecular polymers – TemplaSup

Over the past 25 years, supramolecular polymers have emerged as an entirely new class of dynamic and functional materials. However, the control over their size remains a challenge inherent to their kinetic lability and despite the development of some strategies to achieve better defined structures. Some methodologies, including the use of chain stoppers or the introduction of kinetic biases, are inspired by processes used to control the degree of polymerization and the dispersity of covalent polymers. Alternatively, only few examples report the use of a molecular template but these works only occur in aqueous solutions, are limited to the use of water-soluble DNA templates and do not describe any particular function. The TemplaSup project aims at addressing one important scientific question related to supramolecular polymers: is it possible to control precisely their size in order to produce soft self-assembled materials with optimized functions? The general procedure designed to produce size-controlled nanostructures is based on the templated formation of functional supramolecular polymers in organic solvents using monodisperse synthetic covalent polymers as template. As first step, the proposed methodology involves the hybridization of chemically well-defined monomers on a covalent polymer template leading to the formation of a hybrid supramolecular polymer. In a second step, the isolation of the self-assembled structure whose size should be controlled by the one of the template will be done after freezing the supramolecular polymer by covalent polymerization and further detachment from the polymer template that can be recycled for other cycles of hybridization. The method proposed in this project should therefore provide access to supramolecular polymers with greater control over their size and function in a simpler, less expensive and more scalable way than previously reported strategies. In the longer term, it should allow the formation of supramolecular polymers with a precisely controlled sequence, for which no synthetic method is currently available.