Oxometalate and phosphine ligand co-protected silver nanoclusters: Ag28(dppb)6(MO4)4 and Ag32(dppb)12(MO4)4(NO3)4

Abstract

Thiols, alkynyls and phosphines are the most widely used organic ligands to attain atomically precise metal nanoclusters, while oxometalates as inorganic ligands have almost been neglected in this field. Here, we used oxometalates (e.g., MoO₄²⁻ and WO₄²⁻) as protecting ligands along with phosphines, such as 1,4-bis(diphenylphosphino)butane (dppb), to design and synthesize a new class of silver nanoclusters including Ag₂₈(dppb)₆(MoO₄)₄, Ag₂₈(dppb)₆(WO₄)₄ and Ag₃₂(dppb)₁₂(MoO₄)₄(NO₃)₄. Each cluster consists of a two-shell Ag₄@Ag₂₄ core protected by 4 oxometalates. These clusters exhibit similar optical absorption and photoluminescence properties that are not dependent on surface ligands. Furthermore, the electronic structure analysis shows that the clusters are 20-electron “superatoms”. This work demonstrates that oxometalates can play a key role in the formation of silver nanoclusters, and the effect of oxometalates should be considered in the design and synthesis of metal nanoclusters.