Insight into the Effects of Chiral Diphosphine Ligands on the Structure and Optical Properties of the AuCd Nanocluster.

Inorg Chem

Department of Chemistry and Centre for Atomic Engineering of Advanced Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Institutes of Physical Science and Information Technology and Anhui Province Key Laboratory of Chemistry for Inorganic/

Published: May 2022


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Article Abstract

Introduction of chiral ligands has been regarded as an effective strategy to obtain nanoclusters with optical purity. However, how the chiral ligands work is still unclear due to the lack of structural comparison between racemic nanoclusters and the corresponding optically active ones. In this work, three structurally related AuCd nanoclusters, including one racemic and two homochiral nanoclusters, were synthesized, and their crystal structures were characterized using single-crystal X-ray crystallography (SC-XRD). Based on their crystal structures, the origin of the chirality in AuCd was found to be the twist of the kernel and the chiral arrangement of the metal-ligand surface. AuCd protected with chiral ligands exhibits a more twisted kernel than the racemic one. Therefore, the chirality of chiral diphosphine was found to transfer from the ligands to the metal-ligand interface and then to the metal core, inducing its distortion to produce enhanced chirality. In addition, the optical properties including optical absorption and circular dichroism of these structurally related AuCd nanoclusters were compared.

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http://dx.doi.org/10.1021/acs.inorgchem.2c00246DOI Listing

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