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

The synthesis, via a co-reduction method, of the first Pd-containing silver-rich 21-metal-atom nanocluster passivated by dithiolates, [PdAg 20 {S 2 P(O n Pr) 2 } 12 ] ( 1 ), is reported. 1 is an 8 electron superatom isoelectronic to [Ag 21 {S 2 P(O i Pr) 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, [Pd 6 Ag 14 (S){S 2 P(O n Pr) 2 } 12 ] ( 2 ), for the first time. Its X-ray structure exhibits a sulfide-centered Pd 6 Ag 2 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 . Structurally precise palladium doped silver-nanoclusters [PdAg 20 ] and [Pd 6 Ag 14 (S)] stabilized by twelve dithiophosphate ligands have been isolated. The latter is the first example where a hexa-palladium(0) core is embodied within a silver( i ) cluster.