Engineering Ligand Chemistry on Au Nanoclusters: from Unique Ligand Addition to Precisely Controllable Ligand Exchange

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2023 Jul 21

PMID 37476726

Authors

Jiangtao Zhao

Abolfazl Ziarati

Arnulf Rosspeintner

Yanan Wang

Thomas Burgi

Affiliations

Soon will be listed here.

Abstract

Au nanoclusters (NCs) protected by 18 thiol-ligands (AuSR, 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 AuSR NC are scarce. Herein we report the conversion of hydrophobic AuPET (PET = 2-phenylethylthiolate) NCs to AuSR [AuPET(metal complex)] 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 AuPET NCs is metal dependent. Ru and Co complexes preferentially lead to the formation of AuSR 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 AuSR NCs. The photophysical properties of AuPET(Ru complex) are distinctly different from AuPET. The absorption spectrum is drastically changed upon addition of the extra ligand and the photoluminescence quantum yield of AuPET(Ru complex) is 14 times and 3 times higher than that of pristine AuPET and AuPET(Ru complex), respectively. Interestingly, only one surface ligand (PET) could be substituted by the metal complex when neutral AuPET was used for ligand exchange whereas two ligands could be exchanged when starting with negatively charged AuPET. This charge dependence provides a strategy to precisely control the number of exchanged ligands at the surface of NCs.

Citing Articles

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