Revealing structural isomerism in a nanocluster remains significant but challenging. Herein, we have obtained a pair of structural isomers, [Au 9 Ag 12 (SR) 4 (dppm) 6 X 6 ] 3+ -C and [Au 9 Ag 12 (SR) 4 (dppm) 6 X 6 ] 3+ -Ac [dppm = bis(diphenyphosphino)methane; HSR = 1-adamantanethiol/ tert -butylmercaptan; X = Br/Cl; C stands for one of the structural isomers being chiral; Ac stands for another being achiral], that show different structures as well as different chiralities. These structures are determined by single-crystal X-ray diffraction and further confirmed by high-resolution electrospray ionization mass spectrometry. On the basis of the isomeric structures, the most important finding is the different arrangements of the Au 5 Ag 8 @Au 4 metal core, leading to changes in the overall shape of the cluster, which is responsible for structural isomerism. Meanwhile, the two enantiomers of [Au 9 Ag 12 (SR) 4 (dppm) 6 X 6 ] 3+ -C are separated by high-performance liquid chromatography. Our work will contribute to a deeper understanding of the structural isomerism in noble-metal nanoclusters and enrich the chiral nanocluster.
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Jin et al. (2018) studied this question.
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