Journal
ACS NANO
Volume 13, Issue 6, Pages 7127-7134Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acsnano.9b02552
Keywords
monolayer-protected clusters; chiral nanoclusters; chirality transfer; molecular dynamics simulations; Au-38(SR)(24); NMR; TOCSY
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Funding
- University of Geneva
- Swiss National Science Foundation [200020_172511]
- EU Horizon 2020 Marie Sklodowska-Curie Action IF GOLDENSENS [747209]
- Marie Curie Actions (MSCA) [747209] Funding Source: Marie Curie Actions (MSCA)
- Swiss National Science Foundation (SNF) [200020_172511] Funding Source: Swiss National Science Foundation (SNF)
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The transfer of chirality between nanomolecules is at the core of several applications in chiral technology such as sensing and catalysis. However, the origin of this phenomenon and how exactly nanoscale objects transfer chirality to molecules in their vicinity remain largely obscure. Here, we show that the transfer of chirality for the intrinsically chiral gold cluster Au-38(SR)(24) is site dependent; that is, it differs depending on the ligand-binding sites. This is closely related to the dynamic nature of the ligands on the cluster surface. Using a combination of NMR techniques and molecular dynamics simulations, we could assign the four symmetry-unique ligands on the cluster. The study reveals largely different conformational dynamics of the bound ligands, explaining the diverse diastereotopicities observed for the CH2 protons of the ligands. Although chirality is a structural property, our study reveals the importance of dynamics for the transfer of chirality.
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