Benchmark Models for Elucidating Ligand Effects: Thiols Ligated Isostructural Cu₆ Nanoclusters

Abstract Atomically precise copper nanoclusters (Cu NCs) have attracted tremendous attention for their huge potential in many applications. However, the uncertainty of the growth mechanism and complexity of the crystallization process hinder the in‐depth understanding of their properties. In particular, the ligand effect has been rarely explored at the atomic/molecular level due to the lack of feasible models. Herein, three isostructural Cu 6 NCs ligated with diverse mono‐thiol ligands (2‐mercaptobenzimidazole, 2‐mercaptobenzothiazole, and 2‐mercaptobenzoxazole, respectively) are successfully synthesized, which provide an ideal platform to unambiguously address the intrinsic role of ligands. The overall atom‐by‐atom structural evolution process of Cu 6 NCs is mapped out with delicate mass spectrometry (MS) for the first time. It is intriguingly found that the ligands, albeit only atomic difference (NH, O, and S), can profoundly affect the building‐up processes, chemical properties, atomic structures, as well as catalytic activities of Cu NCs. Furthermore, ion‐molecule reactions combined with density functional theory (DFT) calculations demonstrate that the defective sites formed on ligand can significantly contribute to the activation of molecular oxygen. This study provides fundamental insights into the ligand effect, which is vital for the delicate design of high‐efficient Cu NCs‐based catalysts.