Fan Wentao, Yan Nan, Zha Jun, Gu Wanmiao, You Qing, Yang Ying, Zhuang Shengli, Wu Zhikun
Key Laboratory of Materials Physics, Anhui Key Laboratory of Nanomaterials and Nanotechnology, CAS Center for Excellence in Nanoscience, Institute of Solid State Physics, HFIPS, Chinese Academy of Sciences, Hefei 230031, P. R. China.
University of Science and Technology of China, Hefei 230026, P. R. China.
J Phys Chem Lett. 2023 Apr 6;14(13):3216-3221. doi: 10.1021/acs.jpclett.3c00238. Epub 2023 Mar 27.
It is significant but challenging to understand the property evolution of metal nanoclusters by orientated regulation of the electronic structure. Previous research has demonstrated that the optical properties of metal nanoclusters with anisotropic structures are greatly impacted by their longitudinal electronic structure. However, the manipulation of optical properties of metal nanoclusters by regulating their electronic structure through longitudinal dithiolate substitutions has not yet been reported. In this study, we first achieved the longitudinal single-dithiolate replacement of metal nanoclusters and obtained two novel nanoclusters: Au(SPh-Bu)(SCHSCHS) and Au(SPh-Bu)(SCHCHCHS). Both experimental and theoretical results demonstrated the regulation of the electronic structure (dipole moment) in the (longitudinal) and directions, resulting in absorption redshift and photoluminescence (polarity) enhancement. These findings not only deepen the understanding of the property-electronic structure correlation of metal nanoclusters but also provide guidance for their subtle property tuning.
通过对电子结构进行定向调控来理解金属纳米团簇的性质演变具有重要意义，但也具有挑战性。先前的研究表明，具有各向异性结构的金属纳米团簇的光学性质受到其纵向电子结构的极大影响。然而，通过纵向二硫醇盐取代来调控金属纳米团簇的电子结构从而操纵其光学性质的研究尚未见报道。在本研究中，我们首次实现了金属纳米团簇的纵向单二硫醇盐取代，并获得了两种新型纳米团簇：Au(SPh-Bu)(SCHSCHS) 和 Au(SPh-Bu)(SCHCHCHS)。实验和理论结果均表明，在纵向和方向上电子结构（偶极矩）得到了调控，导致吸收红移和光致发光（极性）增强。这些发现不仅加深了对金属纳米团簇性质-电子结构相关性的理解，也为其精细的性质调控提供了指导。
