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[Au25L18] (Au25), [HNEt3]3[Au67L32Cl4] (Au67), [HNEt3]4[Au106L40Cl12] (Au106), L=3,5‐bis(trifluoromethyl)‐phenylacetylide. Au67 and Au106 are new clusters; the structures were determined by X‐ray single‐crystal diffraction. Au67 contains a distorted Au18 Marks decahedron shelled by an irregular Au32 and further protected with two V‐shaped Au2L3, 13 linear AuL2 staples and 4 chlorides. Au67 is the first structurally determined 34e superatomic gold nanocluster. Au106 is composed of 106 Au atoms co‐protected by alkynyls and chlorides. It has a Au79 kernel, like in Au102(p‐MBA)44. The surface structure of Au106 includes 20 linear Au‐alkynyl staples, 5 Cl‐Au‐Cl and 2 Cl‐Au motifs. These three gold nanoclusters show size‐dependent electrochemical properties. [ABSTRACT FROM AUTHOR]