Gram‐Scale Synthesis of N 2 ‐Type Ag 32 Superatomic Molecule and Its Catalytic Reduction of 4‐Nitrophenol

Cluster assembly serves as an effective approach for tuning cluster properties, ‌where the electronic states arising from fused units play a crucial role in property design, thus attracting attention. In this work, we synthesized a Ag 32 cluster via a one‐pot method, featuring a Ag 22 core formed by fusion of two icosahedral Ag 13 units, with the core protected by a crown‐like motif and two Ag 1 S 2 staples. Further analysis reveals that the Ag 22 core harbors 10 free electrons, which are partitioned equally as 5 electrons per icosahedral Ag 13 subunit—constituting the first observation of the minimum electron count (5e) for such a moiety. This 5e/5e partitioning mirrors N 2 , where each N contributes five valence electrons. DFT calculations confirm this analogy, showing that Ag 32 adopts an electronic structure closely akin to N 2 , establishing a superatomic molecular configuration. Remarkably, like N 2 , this cluster also exhibits robust stability under multiple conditions, including acid, alkali, and reducing conditions. Based on its stability, gram‐scale synthesis of the Ag 32 cluster was readily accomplished. Finally, we investigated its catalytic performance using the 4‐nitrophenol reduction as a model reaction, revealing that the Ag 32 cluster exhibited the highest catalytic activity among comparable clusters (5 min vs. >60 min).