Dolamic Igor, Varnholt Birte, Bürgi Thomas
Département de Chimie Physique, Université de Genève, 30 Quai Ernest-Ansermet, 1211 Genève 4, Switzerland.
Nat Commun. 2015 May 11;6:7117. doi: 10.1038/ncomms8117.
The transfer of chirality from one set of molecules to another is fundamental for applications in chiral technology and has likely played a crucial role for establishing homochirality on earth. Here we show that an intrinsically chiral gold cluster can transfer its handedness to an achiral molecule adsorbed on its surface. Solutions of chiral Au38(2-PET)24 (2-PET=2-phenylethylthiolate) cluster enantiomers show strong vibrational circular dichroism (VCD) signals in vibrations of the achiral adsorbate. Density functional theory (DFT) calculations reveal that 2-PET molecules adopt a chiral conformation. Chirality transfer from the cluster to the achiral adsorbate is responsible for the preference of one of the two mirror images. Intermolecular interactions between the adsorbed molecules on the crowded cluster surface seem to play a dominant role for the phenomena. Such chirality transfer from metals to adsorbates likely plays an important role in heterogeneous enantioselective catalysis.
手性从一组分子转移到另一组分子，这对于手性技术的应用至关重要，并且可能在地球上建立同手性的过程中发挥了关键作用。在此，我们展示了一种具有固有手性的金簇能够将其手性传递给吸附在其表面的非手性分子。手性Au38(2-PET)24（2-PET = 2-苯乙基硫醇盐）簇对映体的溶液在非手性吸附质的振动中显示出强烈的振动圆二色性（VCD）信号。密度泛函理论（DFT）计算表明，2-PET分子采取手性构象。从簇到手性吸附质的手性转移导致了两种镜像中的一种出现偏好。在拥挤的簇表面上吸附分子之间的分子间相互作用似乎对该现象起主导作用。这种从金属到手性吸附质的手性转移可能在多相对映选择性催化中发挥重要作用。
