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Spontaneous Breaking and Remaking of the RS–Au–SR Staple in Self-assembled Ethylthiolate/Au(111) Interface C

Gao, Jianzhi, Li, Fangsen, Zhu, Gangqiang, Yang, Zhibo, Lu, Hongbing, Lin, Haiping, Li, Qing, Li, Youyong, Pan, Minghu, Guo, Quanmin
Journal of physical chemistry 2018 v.122 no.34 pp. 19473-19480
ambient temperature, density functional theory, gold, image analysis, ligands, nanogold, physical chemistry, scanning tunneling microscopy
The stability of the self-assembled RS–Au–SR (R = CH₂CH₃)/Au(111) interface at room temperature has been investigated using scanning tunneling microscopy (STM) in conjunction with density functional theory (DFT) and MD calculations. The RS–Au–SR staple, also known as Au-adatom-dithiolate, assembles into staple rows along the [112̅] direction. STM imaging reveals that while the staple rows are able to maintain a static global structure, individual staples within the row are subjected to constant breaking and remaking of the Au–SR bond. The C₂S–Au–SC₂/Au(111) interface is under a dynamic equilibrium and it is far from rigid. DFT/MD calculations show that a transient RS–Au–Au–SR complex can be formed when a free Au atom is added to the RS–Au–SR staple. The relatively high reactivity of the RS–Au–SR staple at room temperature could explain the reactivity of thiolate-protected Au nanoclusters, such as their ability to participate in ligand exchange and intercluster reactions.