Gratious Saniya, Nair Akhil S, Mukherjee Sayani, Kachappilly Neha, Pathak Biswarup, Mandal Sukhendu
School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram, Maruthamala P.O., Trivandrum, Kerala-695551, India.
Discipline of Chemistry, School of Basic Sciences, Indian Institute of Technology Indore, Indore, Madhya Pradesh-453552, India.
J Phys Chem Lett. 2021 Nov 18;12(45):10987-10993. doi: 10.1021/acs.jpclett.1c03266. Epub 2021 Nov 5.
Molecular level understanding of the structural growth patterns and property evolution in nanoclusters (NCs) is crucial for the design and rational synthesis of clusters for specific properties and applications. In this regard, transformation has always been a versatile approach to achieve atomic precision with atomic purity and a deeper understanding of the growth mechanisms of noble metal NCs. To the latter end, we have demonstrated a structural transformation of Au(SPh-Bu) to Au(SPh-Bu) NC, which occurred through the deassembly of an Au(SPh-Bu) fragment. Kinetic studies conducted on the transformation showed that it follows zero-order kinetics with a low activation energy pathway. Theoretical studies demonstrated that this process happens via surface restructuring of the core-ligand interface, which was found to be the rate-determining step of this transformation. Based on this, a plausible mechanistic pathway for the transformation have been proposed which we envision, will provide useful insights into NC structure evolution.
从分子层面理解纳米团簇（NCs）的结构生长模式和性质演变对于设计和合理合成具有特定性质及应用的团簇至关重要。在这方面，转变一直是一种通用方法，可实现原子精度、原子纯度，并更深入地理解贵金属纳米团簇的生长机制。为此，我们展示了Au(SPh-Bu)向Au(SPh-Bu)纳米团簇的结构转变，该转变通过Au(SPh-Bu)片段的拆解发生。对该转变进行的动力学研究表明，它遵循零级动力学且具有低活化能途径。理论研究表明，这一过程通过核-配体界面的表面重构发生，而这被发现是该转变的速率决定步骤。基于此，我们提出了一个合理的转变机理途径，我们设想这将为纳米团簇结构演变提供有用的见解。
