Synthesis, structural characterization and transformation of an eight-electron superatomic alloy, [Au@Ag-19{S2P(OPr)(2)}(12)]

Abstract : Controlling the metal nanoclusters with atomic precision is highly difficult and further studies on their transformation reactions are even more challenging. Herein we report the controlled formation of a silver alloy nanocluster [AuAg19{S2P(OnPr)(2)}(12)] (1) from an Ag-20 template via a galvanic exchange route. X-ray structural analysis reveals that the alloy structure comprises of a gold-centered Ag-12 icosahedron, Au@Ag-12, capped by seven silver atoms. Interestingly upon reacting with one equiv. of silver(I) salt, (1) can transform into a higher nuclearity nanocluster, [Au@Ag-20{S2P(OnPr)(2)}(12)](+) (2). The conversion process is studied via ESI mass spectrometry and P-31 NMR spectroscopy. This kind of size-structural transformation at the single atom level is quite remarkable. Furthermore, the compositions of all the doped nanoclusters (1, 2) were fully characterized with ESI-MS and EDS. The blue shift depicted in the UV-visible and emission spectra of the doped nanoclusters (1, 2) compared with the precursor, Ag-20, demonstrates that the doping atoms have significant effects on the electronic structures.
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Yan-Ru Lin, Pilli V. V. N. Kishore, Jian-Hong Liao, Samia Kahlal, Yu-Chiao Liu, et al.. Synthesis, structural characterization and transformation of an eight-electron superatomic alloy, [Au@Ag-19{S2P(OPr)(2)}(12)]. Nanoscale, Royal Society of Chemistry, 2018, 10 (15), pp.6855-6860. ⟨10.1039/c8nr00172c⟩. ⟨hal-01807074⟩

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