Eight‐Electron Silver and Mixed Gold/Silver Nanoclusters Stabilized by Selenium Donor Ligands

Abstract

AbstractThe first atomically and structurally precise silver‐nanoclusters stabilized by Se‐donor ligands, [Ag20{Se2P(OiPr)2}12] (3) and [Ag21{Se2P(OEt)2}12]+(4), were isolated by ligand replacement reaction of [Ag20{S2P(OiPr)2}12] (1) and [Ag21{S2P(OiPr)2}12]+ (2), respectively. Furthermore, doping reactions of 4 with Au(PPh3)Cl resulted in the formation of [AuAg20{Se2P(OEt)2}12]+ (5). Structures of 3, 4, and 5 were determined by single‐crystal X‐ray diffraction. The anatomy of cluster 3 with an Ag20 core having C3 symmetry is very similar to that of its dithiophosphate analogue 1. Clusters 4 and 5 exhibit an Ag21 and Au@Ag20 core of Oh symmetry composed of eight silver capping atoms in a cubic arrangement and encapsulating an Ag13 and Au@Ag12 centered icosahedron, respectively. Both ligand exchange and heteroatom doping result in significant changes in optical and emissive properties for chalcogen‐passivated silver nanoparticles, which have been theoretically confirmed as 8‐electron superatoms.