Regiochemistry of Thiolate for Selenolate Ligand Exchange on Gold Clusters
Regiochemistry of Thiolate for Selenolate Ligand Exchange on Gold Clusters
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DOI：
10.1021/jacs.8b10013
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发表时间：
2019-01-09
影响因子：
15
通讯作者：
Ackerson, Christopher J.
中科院分区：
文献类型：
--
作者：
Hosier, Christopher A.;Ackerson, Christopher J.
配体交换是金属纳米颗粒的基本反应。对于硫醇盐保护的金纳米粒子，观察到多重对称性和动力学交换环境，但这些之间的相关性尚不清楚。硫属化物钝化金簇上的配体交换的结构研究迄今已揭示了 10% 或更少的引入配体的位置。在一组 13 个晶体结构中，我们揭示了硒醇交换 Au-25(SeR)(18-x)(SR)(x) 簇的硫醇盐中 18 个配体中最多 17 个配体的位置。总的来说，我们发现随着时间的推移，硫醇盐和硒醇盐配体的位置出现了明显的偏好。这项迄今为止最全面的金簇配体交换结构研究证明了溶剂化配体交换、簇之间配体交换以及相当于簇表面配体平移的净反应的结构基础。
Ligand exchange is a fundamental reaction of metal nanoparticles. Multiple symmetry and kinetic exchange environments are observed for thiolate protected gold nanoparticles, but the correlation between these is unclear. Structural study of ligand exchange on chalcogenide passivated gold clusters has so-far revealed the locations of 10% or fewer of incoming ligands. In a set of 13 crystal structures, we reveal the locations of up to 17 ligands of the 18 ligands in thiolate for selenolate exchanged Au-25(SeR)(18-x)(SR)(x) clusters. Overall, we see a distinct preference for the locations of thiolate and selenolate ligands that emerges over time. This most-comprehensive to-date structural study of ligand exchange on gold clusters evidences a structural basis for exchange of solvated ligands, exchange of ligands between clusters, and a net reaction that amounts to translation of ligands on the cluster surface.