Supramolecular Copolymers: Structure and Composition Revealed by Theoretical Modeling

Supramolecular copolymers, non-covalent analogues of synthetic copolymers, constitute a new and promising class of polymers. In contrast to their covalent counterparts, the details of their mechanism of formation, as well as the factors determining their composition and length, are still poorly understood. Here, the supramolecular copolymerization between two slightly structurally different benzene-1,3,5-tricarboxamide (BTA) monomers functionalized with either oligodimethylsiloxane (oDMSi) or alkyl side chains is unraveled by combining experimental and theoretical approaches. By applying the “sergeant-and-soldiers” approach using circular dichroism (CD) experiments, we are able to obtain detailed insights into the structure and composition of these supramolecular copolymers. Moreover, we observe an unexpected chiral induction upon mixing two independently CD-silent solutions of the achiral (soldier) and chiral (sergeant) monomers. We find that the subtle differences in the chemical structure of the two mo...