Solvent-triggered reversible interconversion of all-nitrogen-donor-protected silver nanoclusters and their responsive...

Surface organic ligands are critical in determining the formation and properties of atomically precise metal nanoclusters. In contrast to the conventionally used thiolate, phosphine and alkynyl ligands, the amine ligand dipyridylamine is applied here as a protecting agent in the synthesis of atomically precise metal nanoclusters. We report two homoleptic amido-protected Ag nanoclusters as examples of all-nitrogen-donor-protected metal nanoclusters: [Ag₂₁(dpa)₁₂]SbF₆ (Ag₂₁) and [Ag₂₂(dpa)₁₂](SbF₆)₂ (Ag₂₂) (dpa = dipyridylamido). Single crystal X-ray structural analysis reveals that both clusters consist of a centered-icosahedron Ag₁₃ core wrapped by 12 dpa ligands. The flexible arrangement of the N donors in dpa facilitates the solvent-triggered reversible interconversion between Ag₂₁ and Ag₂₂ due to their very different solubility. The successful use of dpa in the synthesis of well-defined silver nanoclusters may motivate more studies on metal nanoclusters protected by amido type ligands.