Mono- And hexa-palladium doped silver nanoclusters stabilized by dithiolates

Abstract : The synthesis, via a co-reduction method, of the first Pd-containing silver-rich 21-metal-atom nanocluster passivated by dithiolates, [PdAg20{S2P(OnPr)2}12] (1), is reported. 1 is an 8 electron superatom isoelectronic to [Ag21{S2P(OiPr)2}12]+. The doping of Pd in 1 leads to its high stability against degradation in solution and shows red emission in MeTHF at 77 K. In addition, we report the X-ray crystal structure of a multi-palladium doped silver nanocluster, [Pd6Ag14(S){S2P(OnPr)2}12] (2), for the first time. Its X-ray structure exhibits a sulfide-centered Pd6Ag2 rhombohedron surrounded by twelve additional silver atoms with S6 symmetry. The XPS study and DFT calculations indicate that 2 contains Pd(0) and Ag(i) metals. A significant decrease in the electrochemical gap was observed in the SWVs of 2. © 2019 The Royal Society of Chemistry.
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S.K. Barik, T.-H. Chiu, Y.-C. Liu, M.-H. Chiang, F. Gam, et al.. Mono- And hexa-palladium doped silver nanoclusters stabilized by dithiolates. Nanoscale, 2019, 11 (31), pp.14581-14586. ⟨10.1039/c9nr05068j⟩. ⟨hal-02281736⟩



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