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[Ag-20S2P(OR)(2)(12)]: A Superatom Complex with a Chiral Metallic Core and High Potential for Isomerism

Abstract : The synthesis and structural determination of a silver nanocluster [Ag20 {S2 P(OiPr)2 }12 ] (2), which contains an intrinsic chiral metallic core, is produced by reduction of one silver ion from the eight-electron superatom complex [Ag21 {S2 P(OiPr)2 }12 ](PF6 ) (1) by borohydrides. Single-crystal X-ray analysis displays an Ag20 core of pseudo C3 symmetry comprising a silver-centered Ag13 icosahedron capped by seven silver atoms. Its n-propyl derivative, [Ag20 {S2 P(OnPr)2 }12 ] (3), can also be prepared by the treatment of silver(I) salts and dithiophosphates in a stoichiometric ratio in the presence of excess amount of [BH4 ](-) . Crystal structure analyses reveal that the capping silver-atom positions relative to their icosahedral core are distinctly different in 2 and 3 and generate isomeric, chiral Ag20 cores. Both Ag20 clusters display an emission maximum in the near IR region. DFT calculations are consistent with a description within the superatom model of an 8-electron [Ag13 ](5+) core protected by a [Ag7 {S2 P(OR)2 }12 ](5-) external shell. Two additional structural variations are predicted by DFT, showing the potential for isomerism in such [Ag20 {S2 P(OR)2 }12 ] species.
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https://hal-univ-rennes1.archives-ouvertes.fr/hal-01357410
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Submitted on : Friday, February 17, 2017 - 11:15:29 AM
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Rajendra S. Dhayal, Yan-Ru Lin, Jian-Hong Liao, Yuan-Jang Chen, Yu-Chiao Liu, et al.. [Ag-20S2P(OR)(2)(12)]: A Superatom Complex with a Chiral Metallic Core and High Potential for Isomerism. Chemistry - A European Journal, Wiley-VCH Verlag, 2016, 22 (29), pp.9943--9947. ⟨10.1002/chem.201602275⟩. ⟨hal-01357410⟩

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