Gold Fusion: From Au₂₅(SR)₁₈ to Au₃₈(SR)₂₄, the Most Unexpected Transformation of a Very Stable Nanocluster

The study of the molecular cluster Au₂₅(SR)₁₈ has provided a wealth of fundamental insights into the properties of clusters protected by thiolated ligands (SR). This is also because this cluster has been particularly stable under a number of experimental conditions. Very unexpectedly, we found that paramagnetic Au₂₅(SR)₁₈⁰ undergoes a spontaneous bimolecular fusion to form another benchmark gold nanocluster, Au₃₈(SR)₂₄. We tested this reaction with a series of Au₂₅ clusters. The fusion was confirmed and characterized by UV–vis absorption spectroscopy, ESI mass spectrometry, ¹H and ¹³C NMR spectroscopy, and electrochemistry. NMR evidences the presence of four types of ligand and, for the same proton type, double signals caused by the diastereotopicity arising from the chirality of the capping shell. This effect propagates up to the third carbon atom along the ligand chain. Electrochemistry provides a particularly convenient way to study the evolution process and determine the fusion rate constant, which decreases as the ligand length increases. No reaction is observed for the anionic clusters, whereas the radical nature of Au₂₅(SR)₁₈⁰ appears to play an important role. This transformation of a stable cluster into a larger stable cluster without addition of any co-reagent also features the bottom-up assembly of the Au₁₃ building block in solution. This very unexpected result could modify our view of the relative stability of molecular gold nanoclusters