Visualization of Total Synthesis from Au₁₁ to Au₁₃ Nanoclusters

The emergence of geometrically related Au₁₁ and Au₁₃ nanoclusters (NCs), both possessing a valence electron count of 8e, has substantiated the feasibility of chemically preparing reduced metal nanoclusters. Nevertheless, a significant challenge remains: the dynamic transformation pathways governing their structural evolution have remained elusive, severely impeding precise atomic-level control in NCs synthesis. Herein, we present a large conjugated quinoline thiol ligand with protonatable sites, which enables the systematic construction of seven structurally related Au_11-13 NCs. For the first time, this approach achieves continuous visualization of the total synthesis and core-shell evolution process from Au₁₁ to Au₁₃ NCs. Notably, we successfully synthesized and characterized a metastable corner-missing gold icosahedron Au₁₂ NC (Au@Au₁₁) as a key intermediate through crystallographic methods. These advancements provide unprecedented insights into the nucleation mechanism of classical icosahedral Au NCs, particularly by elucidating how ligand-shell modifications precisely influence geometric rearrangement, electronic structure, and functional performance. The stepwise reaction pathways demonstrated in the Au_11-13 NC series illustrate that metal NC synthesis can achieve organic chemistry-level precision when guided by strategic ligand engineering.