Pincer-Ligand-Stabilized Group 10 Metal Nanoclusters:Chirality and Boat–Chair Structural Transformation

Atomically precise metal nanoclusters bridge the gap between metal atoms and metal nanoparticles, providing an ideal platform for correlating the macroscopic properties of metal nanoparticles to their microstructures. In comparison to the rapid development of coin metal nanoclusters, the knowledge on group 10 metal nanoclusters is relatively limited because of their active nature, resulting in the synthetic challenge. In this work, we successfully synthesize three group 10 metal nanoclusters, that is, Ni₃(SNS)₃, Ni₃(SNOS)₃, and Pd₃(SNS)₃, by using the SNS pincer ligands, which well-stabilize the nickel and palladium metal kernels. Intrinsic chirality of the nanoclusters that originated from the asymmetric arrangement of the surface SNS pincer ligands is discovered. Oxidation-induced irreversible transformation from boat-like Ni₃(SNS)₃ to chair-like Ni₃(SNOS)₃ is observed, and the boat/chair structure-dependent reactivity is revealed. The structural features and intriguing properties of Ni₃ and Pd₃ nanoclusters stabilized by the pincer ligand will inspire further research on group 10 metal nanoclusters.