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Abstract Seed-mediated synthesis strategies, in which small gold nanoparticle precursors are added to a growth solution to initiate heterogeneous nucleation, are among the most prevalent, simple, and productive methodologies for generating well-defined colloidal anisotropic nanostructures. However, the size, structure, and chemical properties of the seeds remain poorly understood, which partially explains the lack of mechanistic understanding of many particle growth reactions. Here, we identify the majority component in the seed solution as an atomically precise gold nanocluster, consisting of a 32-atom Au core with 8 halide ligands and 12 neutral ligands constituting a bound ion pair between a halide and the cationic surfactant: Au₃₂X₈[AQA⁺•X^-]₁₂(X = Cl, Br; AQA = alkyl quaternary ammonium). Ligand exchange is dynamic and versatile, occurring on the order of minutes and allowing for the formation of 48 distinct Au₃₂clusters with AQAX (alkyl quaternary ammonium halide) ligands. Anisotropic nanoparticle syntheses seeded with solutions enriched in Au₃₂X₈[AQA⁺•X^-]₁₂show narrower size distributions and fewer impurity particle shapes, indicating the importance of this cluster as a precursor to the growth of well-defined nanostructures. 

Abstract Three multi‐shell metalloid gold clusters of the composition Au₃₂(R₃P)₁₂Cl₈(R=Et,ⁿPr,ⁿBu) were synthesized in a straightforward fashion by reducing R₃PAuCl with NaBH₄in ethanol. The Au₃₂core comprises two shells, with the inner one constituting a tilted icosahedron and the outer one showing a distorted dodecahedral arrangement. The outer shell is completed by eight chloride atoms and twelve R₃P groups. The inner icosahedron shows bond lengths typical for elemental gold while the distances of the gold atoms in the dodecahedral arrangement are in the region of aurophilic interactions. Quantum‐chemical calculations illustrate that the Jahn–Teller effect observed within the cluster core can be attributed to the electronic shell filling. The easily reproducible synthesis, good solubility, and high yields of these clusters render them perfect starting points for further research.