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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)

[Image: see text] 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 enantiomer...

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Autores principales: Truttmann, Vera, 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
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10604085/
https://www.ncbi.nlm.nih.gov/pubmed/37805942
http://dx.doi.org/10.1021/acsnano.3c06568
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author Truttmann, Vera
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
author_facet Truttmann, Vera
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
author_sort Truttmann, Vera
collection PubMed
description [Image: see text] 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. 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 Au(144) cluster, encompassing hierarchical chirality in ligands, staple configuration, and core structure.
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spelling pubmed-106040852023-10-28 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 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 ACS Nano [Image: see text] 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. 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 Au(144) cluster, encompassing hierarchical chirality in ligands, staple configuration, and core structure. American Chemical Society 2023-10-08 /pmc/articles/PMC10604085/ /pubmed/37805942 http://dx.doi.org/10.1021/acsnano.3c06568 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Truttmann, Vera
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
Directing Intrinsic Chirality in Gold Nanoclusters: Preferential Formation of Stable Enantiopure Clusters in High Yield and Experimentally Unveiling the “Super” Chirality of Au(144)
title Directing Intrinsic Chirality in Gold Nanoclusters: Preferential Formation of Stable Enantiopure Clusters in High Yield and Experimentally Unveiling the “Super” Chirality of Au(144)
title_full Directing Intrinsic Chirality in Gold Nanoclusters: Preferential Formation of Stable Enantiopure Clusters in High Yield and Experimentally Unveiling the “Super” Chirality of Au(144)
title_fullStr Directing Intrinsic Chirality in Gold Nanoclusters: Preferential Formation of Stable Enantiopure Clusters in High Yield and Experimentally Unveiling the “Super” Chirality of Au(144)
title_full_unstemmed Directing Intrinsic Chirality in Gold Nanoclusters: Preferential Formation of Stable Enantiopure Clusters in High Yield and Experimentally Unveiling the “Super” Chirality of Au(144)
title_short Directing Intrinsic Chirality in Gold Nanoclusters: Preferential Formation of Stable Enantiopure Clusters in High Yield and Experimentally Unveiling the “Super” Chirality of Au(144)
title_sort directing intrinsic chirality in gold nanoclusters: preferential formation of stable enantiopure clusters in high yield and experimentally unveiling the “super” chirality of au(144)
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10604085/
https://www.ncbi.nlm.nih.gov/pubmed/37805942
http://dx.doi.org/10.1021/acsnano.3c06568
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