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Chirality transfer from gold nanocluster to adsorbate evidenced by vibrational circular dichroism

机译:手性从金纳米团簇向吸附物的转移通过振动圆二色性证明

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摘要

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.
机译:手性从一组分子到另一组分子的转移对于手性技术的应用是基本的,并且可能在建立地球上的手性上起着至关重要的作用。在这里,我们证明了固有的手性金簇可以将其手性转移至吸附在其表面上的非手性分子。手性Au38(2-PET)24(2-PET = 2-苯基乙基硫醇酯)簇对映体的溶液在非手性被吸附物的振动中显示出强振动圆二色性(VCD)信号。密度泛函理论(DFT)计算显示2-PET分子采用手性构象。从团簇向非手性被吸附物的手性转移是两个镜像之一的优先选择的原因。在拥挤的簇表面上吸附的分子之间的分子间相互作用似乎是该现象的主要作用。从金属到吸附物的这种手性转移可能在非均相对映选择性催化中起重要作用。

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