Size Growth of Au₄Cu₄: From Increased Nucleation to Surface Capping

The size conversion of atomically precise metal nanoclusters is fundamental for elucidating structure-property correlations. In this study, copper salt (CuCl)-induced size growth from [Au₄Cu₄(Dppm)₂(SAdm)₅]⁺ (abbreviated as [AuCuS]) to [Au₄Cu₆(Dppm)₂(SAdm)₄Cl₃]⁺ (abbreviated as [AuCuSCl]) (SAdmH = 1-adamantane mercaptan, Dppm = bis-(diphenylphosphino)methane) was investigated via experiments and density functional theory calculations. The [AuCuS] adopts a defective pentagonal bipyramid core structure with surface cavities, which could be easily filled with the sterically less hindered CuCl and CuSCy (i.e., core growth) (HSCy = cyclohexanethiol) but not the bulky CuSAdm. As long as the Au₄Cu₅ framework is formed, ligand exchange or size growth occurs easily. However, owing to the compact pentagonal bipyramid core structure, the latter growth mode occurs only for the surface-capped [Au₄Cu₆(Dppm)₂(SAdm)₄Cl₃]⁺ structure (i.e., surface-capped size growth). A preliminary mechanistic study with density functional theory (DFT) calculations indicated that the overall conversion occurred via CuCl addition, core tautomerization, Cl migration, the second [CuCl] addition, and [CuCl]-[CuSR] exchange steps. And the [Au₄Cu₆(Dppm)₂(SAdm)₄Cl₃]⁺ alloy nanocluster exhibits aggregation-induced emission (AIE) with an absolute luminescence quantum yield of 18.01% in the solid state. This work sheds light on the structural transformation of Au-Cu alloy nanoclusters induced by Cu(I) and contributes to the knowledge base of metal-ion-induced size conversion of metal nanoclusters.