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Issue 9, 2020
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Enantioseparation and chiral induction in Ag29 nanoclusters with intrinsic chirality

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Abstract

The optical activity of a metal nanocluster (NC) is induced either by an asymmetric arrangement of constituents or by a dissymmetric field of a chiral ligand layer. Herein, we unveil the origin of chirality in Ag29 NCs, which is attributed to the intrinsically chiral atomic arrangement. The X-ray crystal structure of a Ag29(BDT)12(TPP)4 NC (BDT: 1,3-benzenedithiol; TPP: triphenylphosphine) manifested the presence of intrinsic chirality in the outer shell capping the icosahedral achiral Ag13 core. The enantiomers of the Ag29(BDT)12(TPP)4 NC are separated by high-performance liquid chromatography (HPLC) using a chiral column for the first time, showing mirror-image circular dichroism (CD) spectra. The CD spectra are reproduced by time-dependent density functional theory (TDDFT) calculations based on enantiomeric Ag29 models with achiral 1,3-propanedithiolate ligands. The mechanism of chiral induction in the synthesis of Ag29(DHLA)12 (DHLA: α-dihydrolipoic acid) NCs with a chiral ligand system is further discussed with the aid of DFT calculations. The use of the enantiomeric DHLA ligand preferentially leads to a one-handed atomic arrangement which is more stable than the opposite one, inducing the enantiomeric excess in the population of intrinsically chiral Ag29 NCs with CD activity.

Graphical abstract: Enantioseparation and chiral induction in Ag29 nanoclusters with intrinsic chirality

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Supplementary files

Article information


Submitted
21 Oct 2019
Accepted
19 Jan 2020
First published
20 Jan 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020,11, 2394-2400
Article type
Edge Article

Enantioseparation and chiral induction in Ag29 nanoclusters with intrinsic chirality

H. Yoshida, M. Ehara, U. D. Priyakumar, T. Kawai and T. Nakashima, Chem. Sci., 2020, 11, 2394
DOI: 10.1039/C9SC05299B

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