Controlled Noncovalent Synthesis of Secondary Supramolecular Polymers.

Dynamic supramolecular polymers, with their functional similarities to classical covalent polymers and their adaptive and self-repairing nature reminiscent of biological assemblies, have emerged as highly promising systems for the design of smart soft materials. Recent advancements in mechanistic investigations and novel synthetic strategies, such as living supramolecular polymerization, have significantly enhanced our ability to control the primary structure of these supramolecular polymers. However, realizing their full functional potential requires expanding their topological diversity in a manner akin to classical polymers as well as achieving precise molecular organization at higher hierarchical levels of self-assembly. In this paper, we present a remarkable advancement in this field, introducing an unprecedented and controlled synthesis of secondary supramolecular polymers. Our innovative strategy combines chirality-controlled surface-catalyzed secondary nucleation and a bioinspired peptide design, effectively stabilizing higher-order assembly. Furthermore, by harnessing this stereoselective nucleation process, we demonstrate the successful synthesis of racemic supramolecular polymers featuring parallelly stacked conglomerate microstructures─a previously unreported topology in synthetic self-assembled systems. Additionally, we elucidate that the extent of secondary supramolecular polymers can be regulated by modulating the enantiomeric excess of the chiral monomers. Consequently, our study unveils new topologies that exhibit enhanced higher-order structural complexity in the realm of supramolecular polymers.