Site Preference in Multimetallic Nanoclusters: Incorporation of Alkali Metal Ions or Copper Atoms into the Alkynyl-Protected Body-Centered Cubic Cluster [Au₇Ag₈(C≡C^tBu)₁₂]⁺

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• 作者：Yu Wang ; Dr. Haifeng Su ; Liting Ren ; Dr. Sami Malola ; Dr. Shuichao Lin ; Prof. Boon K. Teo ; Prof. Hannu Hä ; kkinen and Prof. Nanfeng Zheng
• 刊名：Angewandte Chemie
• 出版年：2016
• 出版时间：November 21, 2016
• 年：2016
• 卷：128
• 期：48
• 页码：15376-15380
• 全文大小：868K
• ISSN：1521-3757

文摘

The synthesis, structure, substitution chemistry, and optical properties of the gold-centered cubic monocationic cluster [Au@Ag₈@Au₆(C≡C^tBu)₁₂]⁺ are reported. The metal framework of this cluster can be described as a fragment of a body-centered cubic (bcc) lattice with the silver and gold atoms occupying the vertices and the body center of the cube, respectively. The incorporation of alkali metal atoms gave rise to [M_nAg_8−nAu₇(C≡C^tBu)₁₂]⁺ clusters (n=1 for M=Na, K, Rb, Cs and n=2 for M=K, Rb), with the alkali metal ion(s) presumably occupying the vertex site(s), whereas the incorporation of copper atoms produced [Cu_nAg₈Au_7−n(C≡C^tBu)₁₂]⁺ clusters (n=1–6), with the Cu atom(s) presumably occupying the capping site(s). The parent cluster exhibited strong emission in the near-IR region (λ_max=818 nm) with a quantum yield of 2 % upon excitation at λ=482 nm. Its photoluminescence was quenched upon substitution with a Na⁺ ion. DFT calculations confirmed the superatom characteristics of the title compound and the sodium-substituted derivatives.