Intracluster ligand rearrangement: an NMR-based thermodynamic study

Article Article scientifique Article Intracluster ligand rearrangement: an NMR-based thermodynamic study eng 2023 2023 author Rosa-Gastaldo Daniele 0000-0002-6396-6035 Department of Physical Chemistry, University of Geneva, 1211 Geneva, Switzerland 968005 author Pupier Marion Department of Organic Chemistry, University of Geneva, 1211 Geneva, Switzerland 812717 Département de chimie organique (CHIOR) author Meshvildishvili Giorgi Department of Organic Chemistry, University of Geneva, 1211 Geneva, Switzerland 959269 author Viger-Gravel Jasmine Department of Organic Chemistry, University of Geneva, 1211 Geneva, Switzerland 936045 Département de chimie organique (CHIOR) author Buergi Thomas 0000-0003-0906-082X Department of Physical Chemistry, University of Geneva, 1211 Geneva, Switzerland 727741 Département de chimie physique (CHIFI) 6838-6843 10.1039/D3NR00360D 36960796 2040-3364 PMC10077333 http://xlink.rsc.org/?DOI=D3NR00360D 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. Dewey 540 Swiss National Science Foundation Monolayer-protected clusters: Chiral amplification, switches and vibrational spectra 192232 CH 38 Département de chimie physique 142 36 Département de chimie organique 141 false 1350 Groupe Viger-Gravel 694 Groupe Bürgi Nanoscale 15 14 5320587a-69b3-4ec0-b3b4-95d7328796ac Article (Published version) Public Article-scientifique-from-crossref.pdf 757668 application/pdf CC BY-3.0 9bffb19f4216157f7003b2df68b5544de6c3f6a10027580734a8cceb86504961 openAccess Faculté des sciences / Section de chimie et biochimie / Département de chimie physique Faculté des sciences / Section de chimie et biochimie / Département de chimie organique

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Intracluster ligand rearrangement: an NMR-based thermodynamic study	Nanoscale			2023	180	336

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