Enriching Structural Diversity of Alkynyl-Protected Gold Nanoclusters with Chlorides.

The synthesis and isolation of alkynyl/chloride-protected gold nanoclusters is described. Silica gel column chromatography is effective in isolating gold nanoclusters from the as-synthesized cluster mixture to give the clusters Na[Au L ] (Au ), [HNEt ] [Au L Cl ] (Au ), [HNEt ] [Au L Cl ] (Au ), L=3,5-bis(trifluoromethyl)-phenylacetylide. Au and Au are new clusters; the structures were determined by X-ray single-crystal diffraction. Au contains a distorted Au Marks decahedron shelled by an irregular Au and further protected with two V-shaped Au L , 13 linear AuL staples and 4 chlorides. Au is the first structurally determined 34e superatomic gold nanocluster. Au is composed of 106 Au atoms co-protected by alkynyls and chlorides. It has a Au kernel, like in Au (p-MBA) . The surface structure of Au includes 20 linear Au-alkynyl staples, 5 Cl-Au-Cl and 2 Cl-Au motifs. These three gold nanoclusters show size-dependent electrochemical properties.