Enhanced Stability and Properties of Benzene-1,3,5-Tricarboxamide Supramolecular Copolymers through Engineered Coupled Equilibria.

Improving the stability of multi-component and functional assemblies such as supramolecular copolymers without impeding their dynamicity is key for their implementation as innovative materials. Up to now, this has been achieved by a trial-and-error approach, requiring the time-consuming characterization of a series of supramolecular coassemblies. We report herein that this is possible to significantly enhance the stability of supramolecular copolymers by a minimal change in the chemical nature of one of the interacting monomers. This is achieved by replacing an ester function by an ether function in the structure of a chiral benzene-1,3,5-tricarboxamide (BTA) monomer, used as "sergeant", coassembled with achiral monomers, the "soldiers". Pseudo-phase diagrams, constructed by probing the nature of the coassemblies with multifarious analytical techniques, confirm that the greater stability of the resulting copolymers is mainly due to the minimization of competing species. This leads to better rheological and catalytic properties of the corresponding supramolecular copolymers. Favouring coassembly over undesired assembly pathways must be considered as a blueprint for the development of better-performing supramolecular multi-component systems.