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Polyoxometalates 2023, 2(4): 9140035 https://doi.org/10.26599/POM.2023.9140035
Research Article | Open Access | Issue | Published: 22 September 2023

Ligand-correlated crystalline assembly of nanoclusters with atomic precision

Show Author's Information Peiyao Pan,  Di Zhang,  Xuejuan Zou( ),  Xi Kang( ),  Manzhou Zhu ( )
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/Organic Hybrid Functionalized Materials, Anhui University, Hefei 230601, China
Keywords:
metal nanoclusters, hierarchical assembly, ligand effect, crystalline arrangement
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Pan P, Zhang D, Zou X, et al. Ligand-correlated crystalline assembly of nanoclusters with atomic precision. Polyoxometalates, 2023, 2(4): 9140035. https://doi.org/10.26599/POM.2023.9140035
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Abstract Full text Electronic supplementary material About this article

Understanding the assembly pattern of metal nanoclusters in crystalline units at the atomic level is crucial for an in-depth understanding of their supramolecular interactions and structure–property correlations. In this study, two Au9Ag6 nanoclusters bearing a similar framework were controllably synthesized and structurally determined. By tailoring the peripheral thiol ligands from SPhpOMe to SPhoMe (HSPhpOMe = 4-methoxythiophenol, HSPhoMe = 2-methylbenzenethiol), the hierarchical assembly of cluster molecules in their superlattice varied from “ABAB” to “ABCDABCD”. Based on the atomically precise structures of the two nanoclusters, we proposed that such differences in crystalline packing modes resulted from a combination of their structural differences, including intramolecular coordination preferences (Au–P vs. Ag–Cl), steric hindrance effects of thiol ligands (SPhpOMe vs. SPhoMe), and intra-/inter-cluster interactions (C–H···π, π···π, and H···H). We also investigated the structure/assembly-dependent optical properties of the two clusters at different states and rationalized the obtained structure–property correlations at the atomic level. Moreover, this study presented an interesting case for analyzing the hierarchical assembly of metal nanoclusters, allowing an in-depth understanding of the ligand effect on the crystalline assemblies of metal nanoclusters with atomic precision.


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Electronic supplementary material
About this article

Ligand-correlated crystalline assembly of nanoclusters with atomic precision

Show Author's information Peiyao Pan, Di Zhang, Xuejuan Zou( ), Xi Kang( ), Manzhou Zhu ( )
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/Organic Hybrid Functionalized Materials, Anhui University, Hefei 230601, China

Abstract

Understanding the assembly pattern of metal nanoclusters in crystalline units at the atomic level is crucial for an in-depth understanding of their supramolecular interactions and structure–property correlations. In this study, two Au9Ag6 nanoclusters bearing a similar framework were controllably synthesized and structurally determined. By tailoring the peripheral thiol ligands from SPhpOMe to SPhoMe (HSPhpOMe = 4-methoxythiophenol, HSPhoMe = 2-methylbenzenethiol), the hierarchical assembly of cluster molecules in their superlattice varied from “ABAB” to “ABCDABCD”. Based on the atomically precise structures of the two nanoclusters, we proposed that such differences in crystalline packing modes resulted from a combination of their structural differences, including intramolecular coordination preferences (Au–P vs. Ag–Cl), steric hindrance effects of thiol ligands (SPhpOMe vs. SPhoMe), and intra-/inter-cluster interactions (C–H···π, π···π, and H···H). We also investigated the structure/assembly-dependent optical properties of the two clusters at different states and rationalized the obtained structure–property correlations at the atomic level. Moreover, this study presented an interesting case for analyzing the hierarchical assembly of metal nanoclusters, allowing an in-depth understanding of the ligand effect on the crystalline assemblies of metal nanoclusters with atomic precision.

Keywords: metal nanoclusters, hierarchical assembly, ligand effect, crystalline arrangement

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Publication history

Received: 26 June 2014
Revised: 27 August 2023
Accepted: 08 September 2023
Published: 22 September 2023
Issue date: December 2023

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© The Author(s) 2023. Polyoxometalates published by Tsinghua University Press.

Acknowledgements

Acknowledgements

We acknowledge the financial support of the National Natural Science Foundation of China (Nos. 21631001, 21871001, 22101001, and 22201001), the Ministry of Education, the University Synergy Innovation Program of Anhui Province (No. GXXT-2020-053), and the Scientific Research Program of Universities in Anhui Province (No. 2022AH030009).

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