Citation: Xin Zhang, Hua-Yan Yang, Xiao-Jing Zhao, Yu Wang, Nan-Feng Zheng. The effects of surface ligands and counter cations on the stability of anionic thiolated M₁₂Ag₃₂ (M=Au, Ag) nanoclusters[J]. Chinese Chemical Letters, ;2014, 25(6): 839-843. doi: 10.1016/j.cclet.2014.05.027 shu

The effects of surface ligands and counter cations on the stability of anionic thiolated M₁₂Ag₃₂ (M=Au, Ag) nanoclusters

Xin Zhang ^a,b ,
Hua-Yan Yang ^a,b ,
Xiao-Jing Zhao ^a,b ,
Yu Wang ^a,b ,
Nan-Feng Zheng ^a,b,,

1.
a State Key Laboratory for Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen 361005, China;
2.
b Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China

Corresponding author: Nan-Feng Zheng,
Received Date: 30 April 2014
Available Online: 9 May 2014
Fund Project: We thank the MOST of China (No. 2011CB932403) (No. 2011CB932403)the NSFC of China (Nos. 21131005, 21390390, 21333008) for financial support. (Nos. 21131005, 21390390, 21333008)

The stabilities of [M₁₂Ag₃₂(SR)₃₀]^4- (M=Ag, Au and SR=SPhF₂, SPhCF₃, SPhF) clusters having the same structure but different surface ligands or counter cations were systematically studied. It was clearly revealed that a subtle structural change in the surface ligands or counter cations could significantly alter the overall stability of [M₁₂Ag₃₂(SR)₃₀]^4- although they all had an electronic structure of 18-electron superatom shell closure. SPhCF₂ was found as a better surface ligand than SPhCF₃ or SPhF to stabilize [M₁₂Ag₃₂(SR)₃₀]^4-. And the use of more bulky [(PPh₃)₂N]⁺ as the counter cations was revealed to bemore deleterious to the overall stability of [M₁₂Ag₃₂(SR)₃₀]^4- clusters than PPh₄⁺. [Au₁₂Ag₃₂(SR)₃₀]^4- was muchmore stable than [Ag₄₄(SR)₃₀]^4- with the same surface ligands and counter cations. An exceptional stability was observed on (PPh₄)₄[Au₁₂Ag₃₂(SPhCF₂)₃₀] which was stable in DMF for more than 8 days in air at 80℃. More research efforts are still needed to deeply understand why a small structural change could result in a significant change in the stability of noble metal nanoclusters.
- Nanoclusters,
- Stability,
- Ligand effect,
- Noble metal
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The effects of surface ligands and counter cations on the stability of anionic thiolated M12Ag32 (M=Au, Ag) nanoclusters

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通讯作者: 陈斌, bchen63@163.com

The effects of surface ligands and counter cations on the stability of anionic thiolated M₁₂Ag₃₂ (M=Au, Ag) nanoclusters