Journal
NANOSCALE
Volume 11, Issue 31, Pages 14581-14586Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c9nr05068j
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Funding
- Ministry of Science and Technology in Taiwan [MOST 106-2113-M-259-010]
- ANR-MOST 2018 program (project Nanoalloys)
- GENCI computer resource center [A0030807367]
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The synthesis, via a co-reduction method, of the first Pd-containing silver-rich 21-metal-atom nanocluster passivated by dithiolates, [PdAg20{S2P((OPr)-Pr-n)(2)}(12)] (1), is reported. 1 is an 8 electron superatom isoelectronic to [Ag-21{S2P((OPr)-Pr-i)(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((OPr)-Pr-n)(2)}(12)] (2), for the first time. Its X-ray structure exhibits a sulfide-centered Pd6Ag2 rhombohedron surrounded by twelve additional silver atoms with S-6 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.
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