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

Megalamane S Bootharaju; Hogeun Chang; Guocheng Deng; Sami Malola; Woonhyuk Baek; Hannu Häkkinen; Nanfeng Zheng; Taeghwan Hyeon

doi:10.1021/jacs.9b03257

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

J Am Chem Soc. 2019 May 29;141(21):8422-8425. doi: 10.1021/jacs.9b03257. Epub 2019 May 17.

Authors

Megalamane S Bootharaju^{1

2}, Hogeun Chang^{1

2}, Guocheng Deng³, Sami Malola⁴, Woonhyuk Baek^{1

2}, Hannu Häkkinen⁴, Nanfeng Zheng³, Taeghwan Hyeon^{1

2}

Affiliations

¹ Center for Nanoparticle Research , Institute for Basic Science (IBS) , Seoul 08826 , Republic of Korea.
² School of Chemical and Biological Engineering, and Institute of Chemical Processes , Seoul National University , Seoul 08826 , Republic of Korea.
³ Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Department of Chemistry, College of Chemistry and Chemical Engineering , Xiamen University , Xiamen 361005 , China.
⁴ Departments of Physics and Chemistry, Nanoscience Center , University of Jyväskylä , FI-40014 Jyväskylä , Finland.

PMID: 31083937
DOI: 10.1021/jacs.9b03257

Abstract

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.