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While there are numerous recent reports on doping of a ligand-protected noble metal nanocluster (e.g., Au and Ag) with another noble metal, non-noble metal (e.g., Cd) doping remains challenging. Here, we design a phosphine-assisted synthetic strategy and synthesize a Cd doped Ag nanocluster, Cd 12 Ag 32 (SePh) 36 (SePh: selenophenolate), which exhibits characteristic UV-vis absorption features and rare near-infrared (NIR) photoluminescence at ∼1020 nm. The X-ray single crystal structure reveals an asymmetric two-shell Ag 4 @Ag 24 metal kernel protected by four nonplanar Cd 3 Ag(SePh) 9 metal-ligand frameworks. Furthermore, the electronic structure analysis shows that the cluster is a 20-electron "superatom" and density functional theory predicts that its chiral optical response is comparable to the well-known Au 38 (SR) 24 cluster. Our synthetic approach will pave a new path for introducing other non-noble metals into noble metal nanoclusters for exploring their effect on optical and chemical properties.

Cd12Ag32(SePh)36: Non-Noble Metal Doped Silver Nanoclusters

Cd₁₂Ag₃₂(SePh)₃₆: Non-Noble Metal Doped Silver Nanoclusters