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]<sup/>.
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.
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, 361005, China.
Yu
Y
Wang
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, 361005, China.
Haifeng
H
Su
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, 361005, China.
Liting
L
Ren
Departments of Physics and Chemistry, Nanoscience Center, University of Jyväskylä, Jyväskylä, 40014, Finland.
Sami
S
Malola
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, 361005, China.
Shuichao
S
Lin
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, 361005, China.
Boon K
BK
Teo
Departments of Physics and Chemistry, Nanoscience Center, University of Jyväskylä, Jyväskylä, 40014, Finland.
Hannu
H
Häkkinen
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, 361005, China.
Nanfeng
N
Zheng
alkali metals; alkynes; doping; nanoclusters; superatoms