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Site Preference in Multimetallic Nanoclusters: Incorporation of Alkali Metal Ions or Copper Atoms into the Alkynyl‐Protected Body‐Centered Cubic Cluster [Au 7 Ag 8 (C≡C t Bu) 12 ] +
Author(s) -
Wang Yu,
Su Haifeng,
Ren Liting,
Malola Sami,
Lin Shuichao,
Teo Boon K.,
Häkkinen Hannu,
Zheng Nanfeng
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201609144
Subject(s) - alkali metal , nanoclusters , chemistry , crystallography , cluster (spacecraft) , copper , metal , atom (system on chip) , stereochemistry , organic chemistry , computer science , programming language , embedded system
The synthesis, structure, substitution chemistry, and optical properties of the gold‐centered cubic monocationic cluster [Au@Ag 8 @Au 6 (C≡C t Bu) 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 n Ag 8− n Au 7 (C≡C t Bu) 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 n Ag 8 Au 7− n (C≡C t Bu) 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.