Cd12Ag32(SePh)36 : Non-Noble Metal Doped Silver Nanoclusters
Bootharaju, M. S., Chang, H., Deng, G., Malola, S., Baek, W., Häkkinen, H., . . . , & Hyeon, T. (2019). Cd12Ag32(SePh)36 : Non-Noble Metal Doped Silver Nanoclusters. Journal of the American Chemical Society, 141 (21), 8422-8425. doi:10.1021/jacs.9b03257
Published inJournal of the American Chemical Society
© 2019 American Chemical Society.
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, Cd12Ag32(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 Ag4@Ag24 metal kernel protected by four nonplanar Cd3Ag(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 Au38(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. ...