Fluorinated Aromatic Amide Helices: Synthesis and Modeling of Helical Handedness

We present a next-generation helical polyamide synthesized from 5-amino-2,4-difluorobenzoic acid. Polymerization, driven by chloro-tritolylphosphonium iodide (PHOS3), achieved precise molecular weight control and narrow dispersity. Introducing (R) and (S) chiral initiators successfully induced well-defined helical structures, as confirmed by distinct Cotton effects with opposing signs. Molecular dynamics simulations provided deeper insight into the self-assembly process of two helices adopting opposite helicities (P and M). Notably, S–M helices formed compact, highly cohesive, noncovalent stacks, demonstrating packing efficiency over their S–P counterparts. These findings enhance our understanding of polymer chirality, molecular organization, and self-assembly, paving the way for the rational design of advanced helical materials with promising applications in materials science.