Han Wenhua, Wang Endong, Xu Wen Wu
Department of Physics, School of Physical Science and Technology, Ningbo University, Ningbo, 315211, China.
School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian, 116029, China.
Phys Chem Chem Phys. 2022 Jul 6;24(26):15920-15924. doi: 10.1039/d2cp00421f.
This study presents thorough structural insights into the stability of crystallized Au(SAdm) (HSAdm = 1-adamantanethiol) nanocluster. With the recently developed Ring Model for describing the interaction between inner gold cores and outer protecting ligands in thiolate-protected gold nanoclusters, the experimental spontaneous transformation from the crystallized Au(SAdm) to Au(SAdm) could be well understood as structurally unfavorable for the current Au(SAdm) and could also be attributed to the weaker aurophilic interaction between the inner Au core and the surrounding rings in Au(SAdm) over that in Au(SAdm). Furthermore, with the Ring Model and the grand unified model, two new Au(SCH) isomers with evident lower energies, higher HOMO-LUMO gaps as well as distinct optical properties over the available crystallized isomer were obtained. This study deepens the current knowledge on the structure of the Au(SR) cluster from a new structural point of view and also confirms the validity as well as practicability of the Ring Model in understanding and predicting the stable structures of thiolate-protected gold nanoclusters.
本研究对结晶态的Au(SAdm)（HSAdm = 1-金刚烷硫醇）纳米团簇的稳定性进行了深入的结构解析。利用最近开发的环模型来描述硫醇盐保护的金纳米团簇中内部金核与外部保护配体之间的相互作用，结晶态的Au(SAdm)到Au(SAdm)的实验性自发转变可以很好地理解为从结构上看对当前的Au(SAdm)不利，并且这也可归因于Au(SAdm)中内部金核与周围环之间的亲金相互作用比Au(SAdm)中的更弱。此外，利用环模型和大统一模型，获得了两种新的Au(SCH)异构体，它们的能量明显更低，HOMO-LUMO能隙更高，并且与现有的结晶异构体相比具有独特的光学性质。本研究从新的结构角度加深了当前对Au(SR)团簇结构的认识，同时也证实了环模型在理解和预测硫醇盐保护的金纳米团簇稳定结构方面的有效性和实用性。
