Atomically precise Au₁₄₄(SR)₆₀ nanoclusters (R = Et, Pr) are capped by 12 distinct ligand types of 5-fold equivalence...

For two decades, Au₁₄₄(SR)₆₀ has been one of the most studied and used thiolate (SR) protected gold nanoclusters. In many ways, however, it proved to be a challenging and elusive case, also because of the difficulties in solving its structure by single-crystal X-ray crystallography. We used very short thiols and could prepare Au₁₄₄(SC₂H₅)₆₀ and Au₁₄₄(SC₃H₇)₆₀ in a very pure form, which was confirmed by UV-vis absorption spectroscopy and very regular electrochemistry patterns. Inductively coupled plasma and electrospray ionization mass spectrometries gave definite proof of the Au₁₄₄(SR)₆₀ stoichiometry. High-resolution 1D and 2D NMR spectroscopy in the solution phase provided the result of assessing the presence of 12 ligand types in exactly the same amount (5-fold equivalence). Equally important, we found that the two protons belonging to each methylene group along the thiolate chain are diastereotopic. For the α-CH₂ protons, the diastereotopic effect can be indeed gigantic, as it reaches chemical-shift differences of 2.9 ppm. DFT calculations provided insights into the relationship between structure and NMR results. In particular, the 12 ligand types and corresponding diastereotopic effects may be explained by considering the presence of C-H···S hydrogen bonds. These results thus provide fundamental insights into the structure of the thiolate layer capping this long-studied gold nanocluster.