Unlocking Intrinsic Chirality in Luminescent Copper Clusters via Intramolecular Spatial Confinement

Most luminescent clusters that exhibit pronounced chiral signals typically rely on predesigned chiral ligands; however, stimulating the intrinsic chirality of clusters in the absence of exogenous asymmetric ligands remains a significant challenge. In this study, based on a series of structure-correlated Cu2 clusters, we demonstrate that intramolecular spatial confinement effectively induces distortions in flexible ligands, thereby imparting asymmetry to the cluster framework. This molecular asymmetry further determines the orientation of cluster entities during supramolecular assembly, thus enabling the modulation of chirality across this cluster series between inactive (“off”) and active (“on”) states. In addition, these structure-correlated Cu2 clusters display bright and tunable luminescence, allowing for the fabrication of uniform thin films that function as practical scintillation materials for high-resolution X-ray imaging. Collectively, this work provides a novel perspective for regulating the chiroptical properties of metal clusters through the activation of intramolecular spatial confinement and offers valuable insights into the fabrication of cluster-based nanomaterials with tailored photophysical performances.