Heteroatom-Doping Increases Cluster Nuclearity From an [Ag-20] to an [Au3Ag18] Core

Abstract : A templated galvanic exchange performed on [Ag-20{Se2P(OiPr)(2)}(12)] of C-3 symmetry with three equiv Au-I yields a mixture of [Au1+xAg20-x{Se2P(OiPr)(2)}(12)](+) (x = 0-2) from which [Au@Ag-20{Se2P(OiPr)(2)}(12)](+) and [Au@Au2Ag18{Se2P(OiPr)(2)}(12)](+) are successfully characterized to have T and C-1 symmetry, respectively. Crystal structural analyses combined with DFT calculations on the model compounds explicitly demonstrate that the central Ag-0 of Ag-20 being oxidized by Au-I migrates to the protecting atomic shell as a new capping Ag-I, and both second and third Au dopants prefer occupying non-adjacent icosahedron vertices. The differences in symmetry, T and C-1, are manifested in the spatial orientation of their protecting atomic shell composed of eight capping Ag atoms as well as re-construction upon the replacement of Ag atoms on the vertices of AuAg12 icosahedral core with second and third Au dopants. As a result, a unique pathway for substitutional-doped clusters with increased nuclearity is proposed.
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Wan-Ting Chang, Sachil Sharma, Jian-Hong Liao, Samia Kahlal, Yu-Chiao Liu, et al.. Heteroatom-Doping Increases Cluster Nuclearity From an [Ag-20] to an [Au3Ag18] Core. Chemistry - A European Journal, Wiley-VCH Verlag, 2018, 24 (54), pp.14352-14357. ⟨10.1002/chem.201802679⟩. ⟨hal-01902032⟩

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