Supramolecular Assembly-Driven Emergent Chirality with Simultaneous Induction and Ligand Inversion in Atomic Clusters

Controlling chirality in nanoscale systems remains a fundamental challenge, particularly in intrinsically achiral platforms where both chiral induction and structural reconfiguration are difficult to achieve. Herein, we report a supramolecular assembly-driven strategy that enables simultaneous chiral induction, amplification, and ligand-level inversion in an initially achiral gold nanocluster system. Upon interaction with glutathione (GSH), the nanoclusters undergo hierarchical assembly into fluorescent fibrillar architectures accompanied by the emergence of strong chiroptical activity. Remarkably, the intrinsic chirality of GSH is inverted during the assembly process, revealing a unique coupling between ligand reorganization and nanocluster assembly. Spectroscopic, microscopic, and computational studies collectively indicate that ligand exchange and cooperative noncovalent interactions drive the formation of the assembled state and the associated chiroptical response. This assembly-induced reconfiguration also leads to enhanced fluorescence and amplified chiral signals. Overall, this work establishes supramolecular assembly as a powerful approach for programming emergent chirality in atomically precise nanoclusters and provides a versatile framework for the design of adaptive chiral nanomaterials.