Intracluster ligand rearrangement: an NMR-based thermodynamic study. Issue 14 (24th March 2023)

• Record Type: Journal Article
• Authors: Rosa-Gastaldo, Daniele; Pupier, Marion; Meshvildishvili, Giorgi; Viger-Gravel, Jasmine; Bürgi, Thomas
• Is Part Of: Nanoscale. Volume 15:Issue 14(2023)
• Page Start: 6838
• Page End: 6843
• Publication Date: 2023-03-24
• Subjects: Nanoscience -- Periodicals; Nanotechnology -- Periodicals; 620.505
• DOI: 10.1039/d3nr00360d
• Languages: English
• ISSNs: 2040-3364

Abstract

Abstract : Combining variable-temperature NMR experiments and dynamic-NMR simulations, we extract the thermodynamic activation parameters of a new exchange reaction on atomically precise metal nanoclusters: the intracluster ligand rearrangement reaction (LRR). 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 [Ag24 Au(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.