New stable isomorphous Ag34 and Ag33Au nanoclusters with an open shell electronic structure.

A novel atom-precise 3-electron homosilver nanocluster (Ag34) has been assembled for the first time by the oxidation of a thiol. When adding AuPPh3Cl in the reaction, we obtained an alloyed Ag33Au nanocluster, which shares a similar framework as that of Ag34, in which a doping Au atom replaced a core silver atom. Notably, both Ag34 and alloyed Ag33Au demonstrated exceptional stability in solution and solid state over 3 months, which is difficult to explain by using the superatom model. Such Ag34 and Ag33Au complexes complement the nanoclusters with an open shell electronic structure and unveil a new approach to synthesize monodisperse nanoclusters under mild conditions.