Issue 31, 2023

Control over product formation and thermodynamic stability of thiolate-protected gold nanoclusters through tuning of surface protecting ligands

Abstract

Surface-protecting ligands can regulate the structure of a cluster's core either through electronic or steric effects. However, the influence of the steric effect along with the electronic effect over controlling the structure during ligand exchange reactions remains elusive. To understand this, we have carried out ligand exchange on [Au23(CHT)16] (CHT: cyclohexane thiol) using aromatic thiolates where we have tuned the bulkiness at the para position of the thiolate group on the incoming ligands. The outcome of the experiments reveals that each of the ligands in the chosen series is precisely selective towards the parent cluster transformation through specific intermediates. The ligand with more steric crowding directed the reaction pathway to have Au28 nanocluster as the major product while Au36 was the final product obtained with the gradual decrease of bulkiness over the ligand. The combined experimental and theoretical results elucidated the mechanism of the reaction pathways, product formation, and their stability. Indeed, this study with the series of ligands will add up to the ligand library, where we can decide on the ligand to obtain our desired cluster for specific applications through the ligand exchange reaction.

Graphical abstract: Control over product formation and thermodynamic stability of thiolate-protected gold nanoclusters through tuning of surface protecting ligands

Supplementary files

Article information

Article type
Paper
Submitted
03 Jūn. 2023
Accepted
05 Jūl. 2023
First published
06 Jūl. 2023
This article is Open Access
Creative Commons BY-NC license

Nanoscale, 2023,15, 13102-13109

Control over product formation and thermodynamic stability of thiolate-protected gold nanoclusters through tuning of surface protecting ligands

M. P. Maman, E. Nida Nahan, G. Suresh, A. Das, A. S. Nair, B. Pathak and S. Mandal, Nanoscale, 2023, 15, 13102 DOI: 10.1039/D3NR02617E

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