A Two-Electron Silver Superatom Isolated from Thermally Induced Internal Redox Reactions of A Silver(I) Hydride.

Rational syntheses under controllable reducing conditions in the preparation of superatoms with cluster electron not exceeding two are challenging. Herein a dithiolate-stabilized two-electron silver nanocluster, Ag 10 {S 2 P(O i Pr) 2 } 8 ( 1 ), is isolated via a self-redox reaction of Ag 7 (H){S 2 P(O i Pr) 2 } 6 without adding extra reducing agents. The metal framework of Ag 7 , a bicapped trigonal bipyramid, is highly correlated to that of Ag 10 , suggesting Ag 7 (H){S 2 P(O i 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 1Px ® 1S nature. 1 is highly luminescent at ambient temperature and its triplet emission origin, corresponding to a 1P x → 1S transition, is fully reproduced by TD-DFT calculations.