Bestowing chirality to metals is central in fields such as heterogeneous catalysis and modern optics. Although the bulk phase of metals is symmetric, their surfaces can become chiral through adsorption of molecules. Interestingly, even achiral molecules can lead to locally chiral, though globally racemic, surfaces. A similar situation can be obtained for metal particles or clusters. Here we report the first separation of the enantiomers of a gold cluster protected by achiral thiolates, Au38(SCH2CH2Ph)24, achieved by chiral high-performance liquid chromatography. The chirality of the nanocluster arises from the chiral arrangement of the thiolates on its surface, forming 'staple motifs'. The enantiomers show mirror-image circular dichroism responses and large anisotropy factors of up to 4×10−3. Comparison with reported circular dichroism spectra of other Au38 clusters reveals that the influence of the ligand on the chiroptical properties is minor.

Size exclusion chromatography (SEC) on a semipreparative scale (10 mg and more) was used to size-select ultrasmall gold nanoclusters (<2 nm) from polydisperse mixtures. In particular, the ubiquitous byproducts of the etching process toward Au(38)(SR)(24) (SR, thiolate) clusters were separated and gained in high monodispersity (based on mass spectrometry). The isolated fractions were characterized by UV-vis spectroscopy, MALDI mass spectrometry, HPLC, and electron microscopy. Most notably, the separation of Au(38)(SR)(24) and Au(40)(SR)(24) clusters is demonstrated.

Thiolate-protected gold nanoparticles and clusters combine size-dependent physical properties with the ability to introduce (bio)chemical functionality within their ligand shell. The engineering of the latter with molecular precision is an important prerequisite for future applications. A key question in this respect concerns the flexibility of the gold-sulfur interface. Here we report the first study on racemization of an intrinsically chiral gold nanocluster, Au38(SCH2CH2Ph)24, which goes along with a drastic rearrangement of its surface involving place exchange of several thiolates. This racemization takes place at modest temperatures (40-80 °C) without significant decomposition. The experimentally determined activation energy for the inversion reaction is ca. 28 kcal/mol, which is surprisingly low considering the large rearrangement. The activation parameters furthermore indicate that the process occurs without complete Au-S bond breaking.

Chirality unveiled: Thiolate-protected Au40(SR)24 clusters were enantioenriched using an HPLC approach. CD spectra show strong mirror-image responses, indicating the intrinsic chirality of a cluster of unknown structure protected with achiral ligands

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.