Combining the Single-Atom Engineering and Ligand-Exchange Strategies: Obtaining the Single-Heteroatom-Doped Au₁₆Ag₁(S-Adm)₁₃ Nanocluster with Atomically Precise Structure

Obtaining cognate single-heteroatom doping is highly desirable but least feasible in the research of nanoclusters (NCs). In this work, we reported a new Au 16 Ag 1 (S-Adm) 13 NC, which is synthesized by the combination of single-atom engineering and ligand-exchange strategies. This new NC is so far the smallest crystallographically characterized Au-based NC protected by thiolate. The Au 16 Ag 1 (S-Adm) 13 exhibited a tristratified Au 3 –Au 2 Ag 1 –Au 1 kernel capped by staple-like motifs including one dimer and two tetramers. In stark contrast to the size-growth from Au 18 (S–C 6 H 11 ) 14 to Au 21 (S-Adm) 15 via just the ligand-exchange method, combining single Ag doping on Au 18 (S–C 6 H 11 ) 14 resulted in the size-decrease from Au 17 Ag 1 (S–C 6 H 11 ) 14 to Au 16 Ag 1 (S-Adm) 13 . DFT calculations were performed to both homogold Au 18 and single-heteroatom-doped Au 17 Ag 1 to explain the opposite results under the same ligand-exchange reaction. Our work is expected to inspire the synthesis of new cognate single-atom-doped NCs by combining single-atom engineering and ligand-exchange strategies and also shed light on extensive understanding of the metal synergism effect in the NC range.