A pair of propeller‐like chiral trinuclear CuI clusters (R/S‐Cu3) with unique photoinduced fluorescence enhancement were prepared. R/S‐Cu3 showed intense variable luminescence after UV light irradiation, which was attributed to the stepwise oxidation of ligand in the clusters. It exhibited typical aggregation‐induced emission (AIE) (αAIE=17.3). Mechanism studies showed that metal cluster‐centered (MCC) and triplet metal‐to‐ligand charge‐transfer (3MLCT) processes are the origin of the luminescence; the processes are regulated by a restriction of intramolecular motions mechanism in a different state. The chiral structure and AIE feature endow R/S‐Cu3 with remarkable circularly polarized luminescence (glum=2×10−2) in the aggregated state. It shows good capability for producing reactive oxygen species. This work enriches the kinds of atomically precise AIE clusters, gains insight into their luminescence mechanism, and offers the prospect of application in multifunctional materials.

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.

Understanding how the chiral or achiral section in chiral nanostructures contributes to circularly polarized light emission (CPLE) at the atomic level is of fundamental importance. Here, we report two pairs of atomically precise enantiomers of homosilver ( R/S-Ag12Ag32 ) and heterometal ( R/S-Au12Ag32 ) clusters. The geometrical chirality of R/S-Ag12Ag32 arises from the chiral ligand and interface consisting of positive moieties of Ag32(R/S-PS)24. The circular dichroism of R/S-Ag12Ag32 is active, but CPLE-silent. A complete metal change from Ag12 to Au12 in the achiral core section of S2–@M12@S8 engenders isomorphous heterometal R/S-Au12Ag32 , which activates CPLE. We further quantify the contributions of achiral and chiral sections and for the first time unveil that heterometal bonding (Au12-Ag32) at the linkage varies the delocalization of orbitals and proportion of achiral and chiral section in electron transition-involved orbitals, thus activating CPLE. Based on these unique atomically precise homochiral metal clusters, our work provides a new insight into the contributions of achiral and chiral sections to the origin of chiroptical response of chiral metal clusters, paving the way to advance the development of CPLE nanoparticles.

Using polyhedral oligomeric silsesquioxane (POSS) modified by a thiol group as a protected ligand, atom-precise multi-heteorocluster-based dendrimers Ag @POSS (1 a and 1 b) were assembled. Through the reactive -SH groups, six POSS shell ligands stabilize the central 12-core silver(I) cluster by diverse Ag-S interactions. When such Ag @POSS complex was stimulated by different solvents (acetone or tetrahydrofuran), the core Ag silver(I) cluster underwent reversible structural transformation between flattened cubo-octahedral (in 1 a) and normal cubo-octahedral (in 1 b); concomitantly shell POSS clusters rearranged from pseudo-octahedral to quasi-octahedral. Furthermore, the film matrix modified by 1 a or 1 b showed different hydrophobicity.

A pair of atom‐precise chiral silver(I) nanocluster enantiomers (Ag14‐d and Ag14‐l) protected by d‐ and l‐penicillamine ligands is reported. Crystallographic structures reveal that the nanoclusters consist of a S2− template and a chiral Ag14 core stabilized by 12 penicillamine ligands. The penicillamine ligands show two binding fashions: (i) only thiolate coordination, and (ii) thiolate and carboxylate co‐coordination. Meanwhile, the two enantiomers show strong circular dichroism with opposite signals (mirror image relationship) owing to the chiral metallic core induced by chiral ligands, suggesting that the nanoclusters have well‐defined stereostructures as common chiral molecules do. The proton conductivity is also explored due to the existence of both amino groups and carboxylate groups from the penicillamine ligands, which is beneficial to construct H‐bond network for proton transfer.