Site Preference in Multimetallic Nanoclusters: Incorporation of Alkali Metal Ions or Copper Atoms into the Alkynyl‐Protected Body‐Centered Cubic Cluster [Au7Ag8(C≡CtBu)12]+ |
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| Authors: | Yu Wang Dr. Haifeng Su Liting Ren Dr. Sami Malola Dr. Shuichao Lin Prof. Boon K. Teo Prof. Hannu Häkkinen Prof. Nanfeng Zheng |
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| Affiliation: | 1. Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces and Engineering Research Center for Nano-Preparation Technology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China;2. Departments of Physics and Chemistry, Nanoscience Center, University of Jyv?skyl?, Jyv?skyl?, Finland |
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| Abstract: | The synthesis, structure, substitution chemistry, and optical properties of the gold‐centered cubic monocationic cluster [Au@Ag8@Au6(C≡CtBu)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 [MnAg8?nAu7(C≡CtBu)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 [CunAg8Au7?n(C≡CtBu)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 (λmax=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. |
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| Keywords: | alkali metals alkynes doping nanoclusters superatoms |
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