Department of Physical Chemistry, University of Geneva, 1211 Geneva, Switzerland.
Department of Organic Chemistry, University of Geneva, 1211 Geneva, Switzerland.
Nanoscale. 2023 Apr 6;15(14):6838-6843. doi: 10.1039/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 [Ag(DMBT)] and [AgAu(DMBT)] clusters. We report for the first time that this peculiar intracluster modification does not seem to proceed metal-sulphur bond breaking and follows a first-order rate law, being therefore a process independent from the well-described collisional ligand exchange.
配体和金属交换反应是调整原子精确金属纳米团簇性质的有效方法。因此，深入了解控制配体单层动态的机制对于其特定功能化至关重要。通过组合变温 NMR 实验和动态 NMR 模拟，我们提取了新的交换反应的热力学激活参数：[Ag(DMBT)]和[AgAu(DMBT)]团簇中两个对称独特位置之间的配体内簇重排。我们首次报道，这种特殊的内簇修饰似乎不涉及金属-硫键的断裂，并遵循一级反应定律，因此是一种与描述完善的碰撞配体交换无关的过程。
