Evolution of thiolate-stabilized Ag nanoclusters from Ag-thiolate cluster intermediates

The synthesis of atomically precise thiolate-stabilized silver (Ag) nanoclusters is the subject of intense research interest, yet the formation mechanism of such nanoclusters remains obscure. Here, electrospray ionization mass spectrometry is successfully applied to monitor the reaction intermediates formed during the sodium-borohydride-reduction of silver 4-tert-butylbenzenethiolate (AgSPh-tBu). We demonstrate a unique evolution route to thiolate-stabilized Ag nanoclusters mediated by Ag-thiolate clusters. The Ag-thiolate clusters form in the initial stage of reduction contain tens of Ag atoms and similar number of ligands, and they are transformed into Ag₁₇(SPh-tBu)₁₂^3- and Ag₄₄(SPh-tBu)₃₀^4- nanoclusters in the later reduction process. The number of Ag atoms in the Ag-thiolate clusters determines the reaction path to each final nanocluster product. A similar mechanism is found when silver 2,4-dimethylbenzenethiolate (AgSPhMe₂) is used as precursor. This mechanism differs markedly from the long-established bottom-up evolution process, providing valuable new insights into the synthesis of metal nanoclusters.