biostudies-literatureRosa-Gastaldo DSwiss National Science Foundation6838-6843https://www.ebi.ac.uk/biostudies/studies/S-EPMC10077333biostudies-literatureUnknown15(14)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 <i>via</i> metal-sulphur bond breaking and follows a first-order rate law, being NanoscaleIntracluster ligand rearrangement: an NMR-based thermodynamic study.PMC10077333200020200020_192232192232Viger-Gravel JPupier MRosa-Gastaldo DBurgi TMeshvildishvili GfalseIntracluster ligand rearrangement: an NMR-based thermodynamic study.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 <i>via</i> metal-sulphur bond breaking and follows a first-order rate law, being 2023-01-01T00:00:00Z2023 Apr2026-05-28T14:05:28.122Z2024-11-21T09:31:00.419ZS-EPMC100773333696079610.1039/d3nr00360d