Racemization of Chiral Pd2Au36(SC2H4Ph)24: Doping Increases the Flexibility of the Cluster Surface

被引：111

作者：

Barrabes, Noelia ^{[1
]}

Zhang, Bei ^{[1
]}

Buergi, Thomas ^{[1
]}

机构：

[1] Univ Geneva, Dept Phys Chem, CH-1211 Geneva 4, Switzerland

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2014年 / 136卷 / 41期

基金：

瑞士国家科学基金会;

关键词：

GOLD NANOCLUSTERS; LIGAND-EXCHANGE; CIRCULAR-DICHROISM; CRYSTAL-STRUCTURE; THEORETICAL-ANALYSIS; OXIDATION CATALYSIS; SEPARATION; SPECTRA; AU-38; HYDROGENATION;

D O I：

10.1021/ja507189v

中图分类号：

O6 [化学];

学科分类号：

070301 [无机化学];

摘要：

Pd2Au36(SC2H4Ph)(24) clusters have been prepared, isolated and separated in their enantiomers. Compared to the parent Au-38(SC2H4Ph)(24) cluster, the doping leads to a significant change of the circular dichroism spectrum; however, the anisotropy factors are of similar magnitude in both cases. Isolation of the enantiomers allowed us to study the racemization of the chiral cluster, which reflects the flexibility of the ligand shell composed of staple motifs. The doping leads to a substantial lowering of the racemization temperature. The change in activation parameters due to the doping may be solely due to modification of the electronic structure.

引用

页码：14361 / 14364

页数：4

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