A Versatile Strategy for the Controlled Synthesis of Atomically Precise Palladium Nanoclusters

Abstract The study of the structures, applications, and structure‐property relationships of atomically precise metal nanoclusters relies heavily on their controlled synthesis. Although great progress has been made in the controlled synthesis of Group 11 (Cu, Ag, Au) metal nanoclusters, the preparation of Pd nanoclusters remains a grand challenge. Herein, a new, simple, and versatile synthetic strategy for the controlled synthesis of Pd nanoclusters is reported with tailorable structures and functions. The synthesis strategy involves the controllable transformations of Pd₄(CO)₄(CH₃COO)₄ in air, allowing the discovery of a family of Pd nanoclusters with well‐defined structure and high yield. For example, by treating the Pd₄(CO)₄(CH₃COO)₄ with 2,2‐dipyridine ligands, two clusters of Pd₄ and Pd₁₀ whose metal framework describes the growth of vertex‐sharing tetrahedra have been selectively isolated. Interestingly, chiral Pd₄ nanoclusters can be gained by virtue of customized chiral pyridine‐imine ligands, thus representing a pioneering example to shed light on the hierarchical chiral nanostructures of Pd. This synthetic methodology also tolerates a wide variety of ligands and affords phosphine‐ligated Pd nanoclusters in a simple way. It is believed that the successful exploration of the synthetic strategy would simulate the research enthusiasm on both the synthesis and application of atomically precise Pd nanoclusters.