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]+. Issue 48 (3rd November 2016)

• Record Type: Journal Article
• Authors: Wang, Yu; Su, Haifeng; Ren, Liting; Malola, Sami; Lin, Shuichao; Teo, Boon K.; Häkkinen, Hannu; Zheng, Nanfeng
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 48(2016)
• Page Start: 15152
• Page End: 15156
• Publication Date: 2016-11-03
• Subjects: alkali metals -- alkynes -- doping -- nanoclusters -- superatoms; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201609144
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The synthesis, structure, substitution chemistry, and optical properties of the gold‐centered cubic monocationic cluster [Au@Ag8 @Au6 (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 [Mn Ag8− n Au7 (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 [Cun Ag8 Au7− 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. Abstract : Alkali metals meet coinage metals : Alkali metal ions and copper atoms were incorporated into the hexacapped body‐centered cubic cluster [AuAg8 Au6 (C≡C‐ t Bu)12 ] + . Whereas the copper atoms prefer capping sites, the alkali metal ions tend to replace Ag atoms at the vertices. The substitution of one Ag atom with a Na + ion quenched the photoluminescence of the parent compound.