A Two‐Electron Silver Superatom Isolated from Thermally Induced Internal Redox Reaction of A Silver(I) Hydride

Abstract

Rational syntheses under controllable reducing conditions in the preparation of superatoms with cluster electron number not exceeding two are challenging. Herein a dithiolate-stabilized two-electron silver nanocluster, Ag₁₀ {S₂ P(Oⁱ Pr)₂ }₈ (1), is isolated via a self-redox reaction of Ag₇ (H){S₂ P(Oⁱ Pr)₂ }₆ without adding extra reducing agents. The metal framework of Ag₇ , a bicapped trigonal bipyramid, is highly correlated to that of Ag₁₀ , suggesting Ag₇ (H){S₂ P(Oⁱ Pr)₂ }₆ acts as both reducing agent and template in cluster growth. 1 is highly fluorescent at ambient temperature and TD-DFT calculations indicate that the emission is of 1P_x →1S nature.