Conformation‐Matched Symbiotic Noncovalent Sites Facilitated Supramolecular Nanotwists Featuring both P and M Sub‐Helical Domains

Abstract

Abstract Living system can use homochiral blocks to simultaneously fabricate diverse structures with opposite chirality (e.g., right‐handed α‐helices and left‐handed polyproline‐II helices) for maintaining three‐dimensional conformations and functions of biostructures, but realizing this process in artificial systems remains exceptional challenge due to difficulty in constructing precise noncovalent pattern for diverse chirality transfer. Herein, we report a strategy to fabricate helical nanofibers featuring P and M sub‐domains by delicately introducing symbiotic noncovalent sites in the terminal of l ‐phenylalanine derivatives (LCN). Benefiting from the conformation match of LCN, two symbiotic sites (C≡N, Ar─H ortho ) in terminal cyanophenyl group can synergistically form noncovalent with different sites (C≡N⋯H meta ─Ar; Ar─H ortho ⋯N≡C), resulting in a precise noncovalent network. Furthermore, these two noncovalent facilitate the simultaneous formation of M‐type and P‐type domains due to their opposite spatial direction. Similar phenomenon is also observed from symbiotic sites in another terminal hydroxy group (O, H), further confirming an unusual chirality transfer where molecular homochirality propagates to supramolecular domains with opposite handedness. Besides, these helical domains can further cooperatively organize into higher‐order P‐type helices, in which fiber longitudinal axes aligns with the screw axes of noncovalent‐defined helices. This study accelerates the understanding of diverse chirality transfer based on homochirality in nature and takes into a realm of constructing helical nanostructures with diverse sub‐helices by homochiral blocks.