Luminescent Gold(I)–Oleylamine Supramolecular Clusters as Key Intermediates in the Formation of Ultrathin Gold Nanowires From Gold(III) Precursors

The role of ligand–metal complexes in directing nanostructure growth is widely documented for thiolates. By contrast, the importance of Au‐amine intermediate complexes remains less systematically investigated despite the widespread use of amines, particularly oleylamine (OAm), in nanowire synthesis. Combining SAXS, XAS, and photoluminescence analysis, we demonstrate the early formation of gold complexes featuring an Au(III) center coordinated by four N atoms from OAm which rapidly assemble into disc‐shaped gold supramolecular clusters (Au SCs) (∼3 nm in diameter) with long‐range Au···Au correlations, stable for at least 48 h in the absence of a reducing agent. As Au(III) is progressively reduced to Au(I), the gold centers form linear complexes coordinated by two N atoms and the clusters become strongly luminescent, consistent with the development of aurophilic interactions. Adding triisopropylsilane accelerates reduction to Au(0) and reinforces anisotropic interactions, promoting the directional stacking of the disc‐shaped supramolecular clusters into ultrathin gold nanowires (∼1.6 nm in diameter). This framework establishes a distinct pathway from the thiolate archetype, highlighting the critical role of amine ligation in governing precursor persistence and wire‐like morphology. Beyond their mechanistic significance, the luminescent properties of these Au SCs suggest their use as functional materials in their own right.