Unveiling the Synergistic and Perforation-Dominant Self-Assembly Mechanisms of Supramolecular Chiral Helical...

Supramolecular assemblies with chiral helical structures play pivotal roles in biological systems, molecular sensing, chiral nanomaterials, and optoelectronic devices. Understanding the formation mechanisms of such chiral assemblies is essential for the rational design and precise control of their morphologies and functions. However, the complex noncovalent interactions and multiscale assembly pathways pose significant challenges to unveiling the underlying mechanisms. Herein, we introduce a generic patchy-ellipsoid-chain model that enables efficient coarse-grained molecular dynamics simulations to elucidate the assembly kinetics of supramolecular chiral helical microtoroids. Our simulations reveal that the formation of chiral helical microtoroids arises from the synergistic interplay of molecular chirality, directional noncovalent interactions, and solvophobic effects, proceeding through two distinct kinetic pathways: perforation and cyclization. Notably, the perforation pathway predominates due to energetically favorable π-π stacking interactions. This work provides both a robust modeling framework and mechanistic insights into supramolecular chiral self-assembly, offering rational strategies for the design of tailored supramolecular chiral structures.