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.