Exceptionally Stable Dimers and Trimers of Au25 Clusters Linked with a Bidentate Dithiol: Synthesis, Structure and Chirality Study

Author:

Swierczewski Michal1,Cousin Fabrice2,Banach Ewa1,Rosspeintner Arnulf1,Lawson Daku Latevi Max1,Ziarati Abolfazl1,Kazan Rania1,Jeschke Gunnar3,Azoulay Raymond1,Lee Lay‐Theng2,Bürgi Thomas1ORCID

Affiliation:

1. Department of Physical Chemistry University of Geneva 30 Quai Ernest-Ansermet 1211 Geneva 4 Switzerland

2. Laboratoire Léon Brillouin Université Paris-Saclay CEA-Saclay 91191 Gif-sur-Yvette Cedex France

3. Department of Chemistry and Applied Biosciences, ETH Zürich Vladimir-Prelog-Weg 1–5/10 8093 Zürich Switzerland

Abstract

AbstractA bidentate chiral dithiol (diBINAS) is utilised to bridge Au25 nanoclusters to form oligomers. Separation by size allows the isolation of fractions that are stable thanks to the bidentate nature of the linker. The structure of the products is elucidated by small‐angle X‐ray scattering and calculated using density functional theory. Additional structural details are studied by diffusion‐ordered nuclear magnetic resonance spectroscopy, transmission electron microscopy and matrix‐assisted laser desorption/ionization time of flight mass spectrometry. Significant changes in the optical properties are analysed by UV/Vis and fluorescence spectroscopies, with the latter demonstrating a strong emission enhancement. Furthermore, the emergent chiral characteristics are studied by circular dichroism. Due to the geometry constraints of the nanocluster assemblies, diBINAS can be regarded as a templating molecule, taking a step towards the directed self‐assembly of metal clusters.

Funder

Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung

Centro Svizzero di Calcolo Scientifico

Publisher

Wiley

Subject

General Medicine

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