Issue 28, 2023

Engineering ligand chemistry on Au25 nanoclusters: from unique ligand addition to precisely controllable ligand exchange

Abstract

Au25 nanoclusters (NCs) protected by 18 thiol-ligands (Au25SR18, SR is a thiolate ligand) are the prototype of atomically precise thiolate-protected gold NCs. Studies concerning the alteration of the number of surface ligands for a given Au25SR18 NC are scarce. Herein we report the conversion of hydrophobic Au25PET18 (PET = 2-phenylethylthiolate) NCs to Au25SR19 [Au25PET18(metal complex)1] induced by ligand exchange reactions (LERs) with thiolated terpyridine-metal complexes (metal complex, metal = Ru, Fe, Co, Ni) under mild conditions (room temperature and low amounts of incoming ligands). Interestingly, we found that the ligand addition reaction on Au25PET18 NCs is metal dependent. Ru and Co complexes preferentially lead to the formation of Au25SR19 whereas Fe and Ni complexes favor ligand exchange reactions. High-resolution electrospray ionization mass spectrometry (HRESI-MS) was used to determine the molecular formula of Au25SR19 NCs. The photophysical properties of Au25PET18(Ru complex)1 are distinctly different from Au25PET18. The absorption spectrum is drastically changed upon addition of the extra ligand and the photoluminescence quantum yield of Au25PET18(Ru complex)1 is 14 times and 3 times higher than that of pristine Au25PET18 and Au25PET17(Ru complex)1, respectively. Interestingly, only one surface ligand (PET) could be substituted by the metal complex when neutral Au25PET18 was used for ligand exchange whereas two ligands could be exchanged when starting with negatively charged Au25PET18. This charge dependence provides a strategy to precisely control the number of exchanged ligands at the surface of NCs.

Graphical abstract: Engineering ligand chemistry on Au25 nanoclusters: from unique ligand addition to precisely controllable ligand exchange

Supplementary files

Article information

Article type
Edge Article
Submitted
03 3 2023
Accepted
14 6 2023
First published
22 6 2023
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., 2023,14, 7665-7674

Engineering ligand chemistry on Au25 nanoclusters: from unique ligand addition to precisely controllable ligand exchange

J. Zhao, A. Ziarati, A. Rosspeintner, Y. Wang and T. Bürgi, Chem. Sci., 2023, 14, 7665 DOI: 10.1039/D3SC01177A

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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