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Intracluster ligand rearrangement: an NMR-based thermodynamic study

Published inNanoscale, vol. 15, no. 14, p. 6838-6843
Publication date2023
First online date2023
Abstract

Ligand and metal exchange reactions are powerful methods to tailor the properties of atomically precise metal nanoclusters. Hence, a deep understanding of the mechanisms behind the dynamics that rule the ligand monolayer is crucial for its specific functionalization. Combining variable-temperature NMR experiments and dynamic-NMR simulations, we extract the thermodynamic activation parameters of a new exchange reaction: the intracluster ligand rearrangement between the two symmetry-unique positions in [Ag25(DMBT)18] and [Ag24Au(DMBT)18] clusters. We report for the first time that this peculiar intracluster modification does not seem to proceed via metal–sulphur bond breaking and follows a first-order rate law, being therefore a process independent from the well-described collisional ligand exchange.

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Citation (ISO format)
ROSA-GASTALDO, Daniele et al. Intracluster ligand rearrangement: an NMR-based thermodynamic study. In: Nanoscale, 2023, vol. 15, n° 14, p. 6838–6843. doi: 10.1039/D3NR00360D
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ISSN of the journal2040-3364
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Creation11/08/2023 10:30:14 AM
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