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Directing Intrinsic Chirality in Gold Nanoclusters: Preferential Formation of Stable Enantiopure Clusters in High Yield and Experimentally Unveiling the “Super” Chirality of Au$_{144}$

Truttmann, Vera 1; Loxha, Adea; Banu, Rareş; Pittenauer, Ernst; Malola, Sami; Matus, María Francisca; Wang, Yuchen; Ploetz, Elizabeth A.; Rupprechter, Günther; Bürgi, Thomas; Häkkinen, Hannu; Aikens, Christine; Barrabés, Noelia
1 Institut für Technische Chemie und Polymerchemie (ITCP), Karlsruher Institut für Technologie (KIT)

Abstract:

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 Au$_{25}$, Au$_{38}$, and Au$_{144}$ nanoclusters. Notably, this approach leads to the unexpected formation of intrinsically chiral clusters with high yields for chiral Au$_{38}$ and Au$_{144}$ nanoclusters. Experimental evaluation of chiral activity by circular dichroism (CD) spectroscopy corroborates previous theoretical calculations, highlighting the stronger CD signal exhibited by Au$_{144}$ compared to Au$_{38}$ or Au$_{25}$. Furthermore, the formation of a single enantiomeric form is experimentally confirmed by comparing it with intrinsically chiral Au$_{38}$(2-PET)$_{24}$ (2-PET: 2-phenylethanethiol) and is supported theoretically for both Au$_{38}$ and Au$_{144}$. Moreover, the prepared chiral clusters show stability against diastereoisomerization, up to temperatures of 80°C. ... mehr


Verlagsausgabe §
DOI: 10.5445/IR/1000163741
Veröffentlicht am 02.11.2023
Originalveröffentlichung
DOI: 10.1021/acsnano.3c06568
Scopus
Zitationen: 7
Web of Science
Zitationen: 5
Dimensions
Zitationen: 8
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Technische Chemie und Polymerchemie (ITCP)
Publikationstyp Zeitschriftenaufsatz
Publikationsdatum 24.10.2023
Sprache Englisch
Identifikator ISSN: 1936-0851, 1936-086X
KITopen-ID: 1000163741
Erschienen in ACS Nano
Verlag American Chemical Society (ACS)
Band 17
Heft 20
Seiten 20376–20386
Vorab online veröffentlicht am 08.10.2023
Schlagwörter chirality, metal nanoclusters, ligand, gold, yield, intrinsically chiral, density functional theory
Nachgewiesen in Web of Science
Dimensions
Scopus
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