Thiol Ligand-Induced Transformation of Au38(SC2H4Ph)24 to AU36(SPh-t-BU)24

被引:206
作者
Zeng, Chenjie [1 ]
Liu, Chunyan [2 ]
Pei, Yong [2 ]
Jin, Rongchao [1 ]
机构
[1] Carnegie Mellon Univ, Dept Chem, Pittsburgh, PA 15213 USA
[2] Xiangtan Univ, Dept Chem, Key Lab Environm Friendly Chem & Applicat, Minist Educ, Xiangtan 411105, Hunan, Peoples R China
关键词
gold nanoclusters; ligand-induced transformation; disproportionation mechanism; density functional theory; PROTECTED AU-25 CLUSTER; SIZED GOLD NANOCLUSTERS; STRUCTURAL EVOLUTION; MASS-SPECTROMETRY; ELECTRONIC-PROPERTIES; EXCHANGE REACTIONS; CRYSTAL-STRUCTURE; KDA GOLD; NANOPARTICLES; NANOMOLECULES;
D O I
10.1021/nn401971g
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
We report a disproportionation mechanism identified in the transformation of rod-like biicosahedral Au-38(SCH2CH2Ph)(24) to tetrahedral Au-36(TBBT)(24) nanoclusters. Time-dependent mass spectrometry and optical spectroscopy analyses unambiguously map out the detailed size-conversion pathway. The ligand exchange of Au-38(SCH2CH2Ph)(24) with bulkier 4-tert-butylbenzenethiol (TBBT) until a certain extent starts to trigger structural distortion of the initial biicosahedral Au-38(SCH2CH2Ph)(24) structure, leading to the release of two Au atoms and eventually the Au-36(TBBT)(24) nanocluster with a tetrahedral structure, in which process the number of ligands is interestingly preserved. The other product of the disproportionation process, i.e., Au-40(TBBT)(m)(SCH2CH2Ph)(24-m), was concurrently observed as an intermediate, which was the result of addition of two Au atoms and two TBBT ligands to Au-38(TBBT)(m)(SCH2CH2Ph)(24-m). The reaction kinetics on the Au-38(SCH2CH2Ph)(24) to Au-36(TBBT)(24) conversion process was also performed, and the activation energies of the structural distortion and disproportionation steps were estimated to be 76 and 94 kJ/mol, respectively. The optical absorption features of Au36(TBBT)24 are interpreted on the basis of density functional theory simulations.
引用
收藏
页码:6138 / 6145
页数:8
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