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 25 L 18 ] ( Au 25 ), [HNEt 3 ] 3 [Au 67 L 32 Cl 4 ] ( Au 67 ), [HNEt 3 ] 4 [Au 106 L 40 Cl 12 ] ( Au 106 ), L=3,5‐bis(trifluoromethyl)‐phenylacetylide. Au 67 and Au 106 are new clusters; the structures were determined by X‐ray single‐crystal diffraction. Au 67 contains a distorted Au 18 Marks decahedron shelled by an irregular Au 32 and further protected with two V‐shaped Au 2 L 3 , 13 linear AuL 2 staples and 4 chlorides. Au 67 is the first structurally determined 34e superatomic gold nanocluster. Au 106 is composed of 106 Au atoms co‐protected by alkynyls and chlorides. It has a Au 79 kernel, like in Au 102 ( p ‐MBA) 44 . The surface structure of Au 106 includes 20 linear Au‐alkynyl staples, 5 Cl‐Au‐Cl and 2 Cl‐Au motifs. These three gold nanoclusters show size‐dependent electrochemical properties.