Tracking Dual‐Pathway Self‐Assembly via Butterfly‐Motion‐Based Molecular Fragment Conformational Transformation in Aqueous Homopolypeptides

Despite the inherent chirality of peptides, the development of peptide‐based luminescent nanomaterials has been impeded by weak fluorescence and unclear self‐assembly mechanisms. Herein, we report a straightforward strategy to direct supramolecular assembly by end‐functionalizing homopolypeptides with a vibration‐induced emission (VIE) motif. This system exhibits dual‐pathway self‐assembly, enabling real‐time monitoring of the assembly process via ratiometric fluorescence changes. Depending on the solvent used, the homopolypeptides self‐organize into either nanotoroids or nanorods, which display distinct CPL properties: the nanotoroids exhibit strong CPL activity, whereas the nanorods are CPL‐silent. This work not only establishes a versatile platform for constructing efficient aqueous CPL‐active nanomaterials but also elucidates the correlation between supramolecular morphology and chiroptical output, paving the way for the rational design of biocompatible chiral luminescent systems.