Ubiquitous 8 and 29 kDa Gold:Alkanethiolate Cluster Compounds: Mass-Spectrometric Determination of Molecular Formulas and Structural Implications

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Abstract
The molecular formulas and charge state distributions of thus-far known ubiquitous alkanethiolate-protected gold clusters with core-masses of 8 and 29 kDa were assessed using electrospray ionization mass spectrometry. The 8 and 29 kDa clusters were determined to be composed of single species, [Au38(SCn)24]z and [Au144(SCn)59]z, respectively, with charge states of z ≥ 0. Possible geometric structures for Au38(SCn)24 and Au144(SCn)59 are discussed, based on the structures of relevant systems that have been recently determined experimentally and theoretically: [Au25(SR)18]− and Au102(SR)44, in which the Au cores are protected by monomers [−SR−Au−SR−] and/or dimers [−SR−Au−SR−Au−SR−]. Their preferential formation and chemical robustness are proposed as being associated with high stability due to geometric factors, while the Au−thiolate interface takes on common motifs regardless of the underlying Au core.

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