[Ag20{S2P(OR)2}12]: A Superatom Complex with a Chiral Metallic Core and High Potential for Isomerism

详细信息    查看全文

• 作者：Dr. Rajendra S. Dhayal ; Yan-Ru Lin ; Jian-Hong Liao ; Yuan-Jang Chen ; Yu-Chiao Liu ; Ming-Hsi Chiang ; Dr. Samia Kahlal ; Jean-Yves Saillard and Prof. C. W. Liu
• 刊名：Chemistry - A European Journal
• 出版年：2016
• 出版时间：July 11, 2016
• 年：2016
• 卷：22
• 期：29
• 页码：9943-9947
• 全文大小：1819K
• ISSN：1521-3765

文摘

The synthesis and structural determination of a silver nanocluster [Ag₂₀{S₂P(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{S₂P(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{S₂P(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{S₂P(OR)₂}₁₂]⁵⁻ external shell. Two additional structural variations are predicted by DFT, showing the potential for isomerism in such [Ag₂₀{S₂P(OR)₂}₁₂] species.