Issue 35, 2022

Bicarbonate insertion triggered self-assembly of chiral octa-gold nanoclusters into helical superstructures in the crystalline state

Abstract

Constructing atomically precise helical superstructures of high order is an extensively pursued subject for unique aesthetic features and underlying applications. However, the construction of cluster-based helixes of well-defined architectures comes with a huge challenge owing to their intrinsic complexity in geometric structures and synthetic processes. Herein, we report a pair of unique P- and M-single stranded helical superstructures spontaneously assembled from R- and S-Au8c individual nanoclusters, respectively, upon selecting chiral BINAP (2,2′-bis(diphenylphosphino)-1,1′-binaphthalene) and hydrophilic o-H2MBA (o-mercaptobenzoic acid) as protective ligands to induce chirality and facilitate the formation of helixes. Structural analysis reveals that the chirality of the Au8c individual nanoclusters is derived from the homochiral ligands and the inherently chiral Au8 metallic kernel, which was further corroborated by experimental and computational investigations. More importantly, driven by the O–H⋯O interactions between (HCO3)2 dimers and achiral o-HMBA ligands, R/S-Au8c individual nanoclusters can assemble into helical superstructures in a highly ordered crystal packing. Electrospray ionization (ESI) and collision-induced dissociation (CID) mass spectrometry of Au8c confirm the hydrogen-bonded dimer of Au8c individual nanoclusters in solution, illustrating that the insertion of (HCO3)2 dimers plays a crucial role in the assembly of helical superstructures in the crystalline state. This work not only demonstrates an effective strategy to construct cluster-based helical superstructures at the atomic level, but also provides visual and reliable experimental evidence for understanding the formation mechanism of helical superstructures.

Graphical abstract: Bicarbonate insertion triggered self-assembly of chiral octa-gold nanoclusters into helical superstructures in the crystalline state

Supplementary files

Article information

Article type
Edge Article
Submitted
21 Jun 2022
Accepted
12 Aug 2022
First published
15 Aug 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2022,13, 10523-10531

Bicarbonate insertion triggered self-assembly of chiral octa-gold nanoclusters into helical superstructures in the crystalline state

W. Si, K. Sheng, C. Zhang, Z. Wang, S. Zhang, J. Dou, L. Feng, Z. Gao, C. Tung and D. Sun, Chem. Sci., 2022, 13, 10523 DOI: 10.1039/D2SC03463H

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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