Chirality Fixation of Ag‐Based Nanoclusters via Co‐Crystallization With Ag–P Complexes: Unlocking Circularly Polarized Luminescence

ABSTRACT Intrinsically chiral metal nanoclusters capped with achiral ligands have attracted extensive attention for their unique circularly polarized luminescence (CPL) and promising optoelectronic and catalytic applications. However, such nanoclusters generally exist as thermodynamically stable racemic mixtures, and the efficient separation and chiral fixation of single enantiomers remain a long‐standing challenge that severely restricts their practical chiroptical applications. Herein, we report a novel co‐crystallization strategy to achieve chiral resolution and CPL activation of racemic metal nanoclusters. A new racemic nanocluster [AuAg 28 (H 2 NC 6 H 4 S) 12 (PPh 3 ) 12 Cl 6 ] 3+ was synthesized, and homochiral single crystals were successfully obtained by co‐crystallization with achiral Ag(PPh 3 ) 3 Cl complexes. The introduced Ag–P complexes provide abundant intermolecular interaction sites, while the phenyl groups induce strong T‐shaped π–π stacking forces that rigidly fix the nanocluster into a single chiral conformation. Benefiting from this supramolecular confinement effect, the homochiral crystals exhibit prominent CPL performance. Furthermore, this strategy can be extended to isostructural Ag 29 nanoclusters; the corresponding co‐crystals also display near‐infrared CPL, while core‐metal substitution achieves ∼50 nm emission redshift. This work reveals an atomic‐scale chiral induction mechanism based on achiral co‐crystallization, offering a facile strategy for the design and regulation of high‐performance chiral luminescent nanomaterials.