A New Class of Atomically Precise, Hydride-Rich Silver Nanoclusters Co-Protected by Phosphines

Thiols and phosphines are the most widely used organic ligands to attain atomically precise metal nanoclusters (NCs). Here, we used simple hydrides (e.g., H^-) as ligands along with phosphines, such as triphenylphosphine (TPP), 1,2-bis(diphenylphosphino)ethane [DPPE], and tris(4-fluorophenyl)phosphine [TFPP] to design and synthesize a new class of hydride-rich silver NCs. This class includes [Ag₁₈H₁₆(TPP)₁₀]²⁺, [Ag₂₅H₂₂(DPPE)₈]³⁺, and [Ag₂₆H₂₂(TFPP)₁₃]²⁺. Our work reveals a new family of atomically precise NCs protected by H^- ligands and labile phosphines, with potentially more accessible active metal sites for functionalization and provides a new set of stable NC sizes with simpler ligand-metal bonding for researchers to explore both experimentally and computationally.