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.