Stepwise Achievement of Circularly Polarized Luminescence on Atomically Precise Silver Clusters

The weakly coordinated anionic nitrate ligands in a centrosymmetric Ag(20) cluster are replaced in a stepwise manner by chiral amino acids and two achiral luminescent sulfonic‐group‐containing ligands while nearly maintaining the original silver(I) cage structure. This surface engineering enables the atomically precise Ag(20) clusters to exhibit the high‐efficiency synergetic effects of chirality and fluorescence, producing rare circularly polarized luminescence among the metal clusters with a large dissymmetry factor of (|g(lum)|) ≈ 5 × 10(−3). This rational approach using joint functional ligands further opens a new avenue to diverse multifunctional metal clusters for promising applications.