Directing Intrinsic Chirality in Gold Nanoclusters : Preferential Formation of Stable Enantiopure Clusters in High Yield and Experimentally Unveiling the “Super” Chirality of Au144
Truttmann, V., Loxha, A., Banu, R., Pittenauer, E., Malola, S., Matus, M. F., Wang, Y., Ploetz, E. A., Rupprechter, G., Bürgi, T., Häkkinen, H., Aikens, C., & Barrabés, N. (2023). Directing Intrinsic Chirality in Gold Nanoclusters : Preferential Formation of Stable Enantiopure Clusters in High Yield and Experimentally Unveiling the “Super” Chirality of Au144. Acs Nano, 17(20), 20376-20386. https://doi.org/10.1021/acsnano.3c06568
Julkaistu sarjassa
Acs NanoTekijät
Päivämäärä
2023Tekijänoikeudet
© The Authors. Published by American Chemical Society
Chiral gold nanoclusters offer significant potential for exploring chirality at a fundamental level and for exploiting their applications in sensing and catalysis. However, their widespread use is impeded by low yields in synthesis, tedious separation procedures of their enantiomeric forms, and limited thermal stability. In this study, we investigated the direct synthesis of enantiopure chiral nanoclusters using the chiral ligand 2-MeBuSH in the fabrication of Au25, Au38, and Au144 nanoclusters. Notably, this approach leads to the unexpected formation of intrinsically chiral clusters with high yields for chiral Au38 and Au144 nanoclusters. Experimental evaluation of chiral activity by circular dichroism (CD) spectroscopy corroborates previous theoretical calculations, highlighting the stronger CD signal exhibited by Au144 compared to Au38 or Au25. Furthermore, the formation of a single enantiomeric form is experimentally confirmed by comparing it with intrinsically chiral Au38(2-PET)24 (2-PET: 2-phenylethanethiol) and is supported theoretically for both Au38 and Au144. Moreover, the prepared chiral clusters show stability against diastereoisomerization, up to temperatures of 80 °C. Thus, our findings not only demonstrate the selective preparation of enantiopure, intrinsically chiral, and highly stable thiolate-protected Au nanoclusters through careful ligand design but also support the predicted “super” chirality in the Au144 cluster, encompassing hierarchical chirality in ligands, staple configuration, and core structure.
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Julkaisija
American Chemical Society (ACS)ISSN Hae Julkaisufoorumista
1936-0851Asiasanat
Julkaisu tutkimustietojärjestelmässä
https://converis.jyu.fi/converis/portal/detail/Publication/193386759
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Open Access is funded by the Austrian Science Fund (FWF). CD spectroscopy was supported by an Innovative Project (RAKI-MINT) granted by TU Wien to Astrid R. Mach-Aigner. N.B. acknowledges support by the Austrian Science Fund (FWF) via grant Elise Richter (V831-N). N.B. and T.B. thank COST Action CA21101 COSY. V.T. thanks the Austrian Marshall Plan Foundation for financially supporting her stay at Kansas State University through a Marshall Plan Scholarship. ...Lisenssi
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