Department of Physical Chemistry, University of Geneva , 30 Quai Ernest-Ansermet, 1211 Geneva 4, Switzerland.
J Am Chem Soc. 2014 Oct 15;136(41):14361-4. doi: 10.1021/ja507189v. Epub 2014 Sep 30.
Pd2Au36(SC2H4Ph)24 clusters have been prepared, isolated and separated in their enantiomers. Compared to the parent Au38(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.
Pd2Au36(SC2H4Ph)24 簇合物已被制备、分离并对映体分离。与母体 Au38(SC2H4Ph)24 簇合物相比，掺杂导致圆二色光谱发生显著变化；然而，两种情况下的各向异性因子的大小相似。对映异构体的分离使我们能够研究手性簇合物的外消旋化，这反映了由基本模式组成的配体壳的灵活性。掺杂导致外消旋化温度显著降低。掺杂引起的活化参数的变化可能仅仅是由于电子结构的修饰。
