Academic Awards 2025 booklet

23 Reducing pathway complexity in crowded environments by increasing disorder Supramolecular polymers (SPs) hold great promise to create functional smart materials with unprecedented properties. Unfortunately, SPs are mostly studied in dilute solutions, and the incorporation of such materials into solid-state devices is a formidable challenge. One way to integrate SPs into bulk materials is to embed them into a covalent polymer matrix by evaporating the solvent from a solution of SPs and covalent polymers. As highlighted in our research, the addition of a covalent polymer to a solution of SPs could create a crowded environment, giving rise to bundling of SP fibers. These kinetic traps can make the processing of SPs into solid state devices difficult (see Figure 1). In this project, we investigated a design strategy of statistically incorporating alkyl chains of different length into the periphery of supramolecular monomers. We report that this strategy could significantly reduce bundling and the formation of kinetic traps in crowded environments (see Figure 2). Moreover, the strategy prevents the change of morphology during the processing of SPs into bulk materials. Finally, we also demonstrate the generality of crowding allowing covalent macromolecules to induce supramolecular polymerization by exclusion volume effects. Figure 1 shows how the self-assembly of triazines is complicated by the presence of macromolecules. Figure 2 shows how monomers with random side chains could reduce crowding induced pathway complexity.