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Issue 23, 2010
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Isolation, structure, and stability of a dodecanethiolate-protected Pd1Au24cluster

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A dodecanethiolate-protected Pd1Au24(SC12H25)18 cluster, which is a mono-Pd-doped cluster of the well understood magic gold cluster Au25(SR)18, was isolated in high purity using solvent fractionation and high-performance liquid chromatography (HPLC) after the preparation of dodecanethiolate-protected palladiumgold bimetal clusters. The cluster thus isolated was identified as the neutral [Pd1Au24(SC12H25)18]0 from the retention time in reverse phase columns and by elemental analyses. The LDI mass spectrum of [Pd1Au24(SC12H25)18]0 indicates that [Pd1Au24(SC12H25)18]0 adopts a similar framework structure to Au25(SR)18, in which an icosahedral Au13 core is protected by six [–S–Au–S–Au–S–] oligomers. The optical absorption spectrum of [Pd1Au24(SC12H25)18]0 exhibits peaks at ∼690 and ∼620 nm, which is consistent with calculated results on [Pd1@Au24(SC1H3)18]0 in which the central gold atom of Au25(SC1H3)18 is replaced with Pd. These results strongly indicate that the isolated [Pd1Au24(SC12H25)18]0 has a core–shell [Pd1@Au24(SC12H25)18]0 structure in which the central Pd atom is surrounded by a frame of Au24(SC12H25)18. Experiments on the stability of the cluster showed that Pd1@Au24(SC12H25)18 is more stable against degradation in solution and laser dissociation than Au25(SC12H25)18. These results indicate that the doping of a central atom is a powerful method to increase the stability beyond the Au25(SR)18 cluster.

Graphical abstract: Isolation, structure, and stability of a dodecanethiolate-protected Pd1Au24 cluster

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Article information

23 Dec 2009
12 Mar 2010
First published
14 Apr 2010

Phys. Chem. Chem. Phys., 2010,12, 6219-6225
Article type

Isolation, structure, and stability of a dodecanethiolate-protected Pd1Au24 cluster

Y. Negishi, W. Kurashige, Y. Niihori, T. Iwasa and K. Nobusada, Phys. Chem. Chem. Phys., 2010, 12, 6219
DOI: 10.1039/B927175A

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