Au25(SEt)18, a Nearly Naked Thiolate-Protected Au25Cluster: Structural Analysis by Single Crystal X-ray Crystallography and Electron Nuclear Double Resonance

X-ray crystallography has been fundamental in discovering fine structural features of ultrasmall gold clusters capped by thiolated ligands. For still unknown structures, however, new tools capable of providing relevant structural information are sought. We prepared a 25-gold atom nanocluster protected by the smallest ligand ever used, ethanethiol. This cluster displays the electrochemistry, mass spectrometry, and UV–vis absorption spectroscopy features of similar Au25clusters protected by 18 thiolated ligands. The anionic and the neutral form of Au25(SEt)18were fully characterized by 1H and 13C NMR spectroscopy, which confirmed the monolayer’s properties and the paramagnetism of neutral Au25(SEt)180. X-ray crystallography analysis of the latter provided the first known structure of a gold cluster protected by a simple, linear alkanethiolate. Here, we also report the direct observation by electron nuclear double resonance (ENDOR) of hyperfine interactions between a surface-delocalized unpaired electron and the gold atoms of a nanocluster. The advantages of knowing the exact molecular structure and having used such a small ligand allowed us to compare the experimental values of hyperfine couplings with DFT calculations unaffected by structure’s approximations or omissions.