Snapshots of key intermediates unveiling the growth from silver ions to Ag70 nanoclusters

Nanoclusters (NCs) are considered as initial states of condensed matter, and unveiling their formation mechanism is of great importance for directional synthesis of nanomaterials. Here, we initiate the reaction of Ag( i ) ions under weak reducing conditions. The prolonged reaction period provides a unique opportunity for revealing the five stages of the growth mechanism of 20-electron superatomic Ag70 NCs by a time-dependent mass technique, that is, aggregate (I) → reduction (II) → decomposition and recombination (III) → fusion (IV) → surface recombination and motif enrichment (V), which is different from the formation process applicable to the gold clusters. More importantly, the key intermediates, Ag14 without free electrons (0e) in the first (stage I) and Ag24 (4e) in the second (stage II), were crystallized and structurally resolved, and the later transformation rate towards Ag70 was further controlled by modulating solvents for easy identification of more intermediates. In a word, we establish a reasonable path of gradual expansion in size and electrons from Ag( i ) ions to medium-sized 20e Ag70. This work provides new insights into the formation and evolution of silver NCs, and unveils the corresponding optical properties along with the process.