Regulating the Electronic Structure of Metal Nanoclusters by Longitudinal Single-Dithiolate Substitution

Wentao Fan; Nan Yan; Jun Zha; Wanmiao Gu; Qing You; Ying Yang; Shengli Zhuang; Zhikun Wu

doi:10.1021/acs.jpclett.3c00238

Regulating the Electronic Structure of Metal Nanoclusters by Longitudinal Single-Dithiolate Substitution

J Phys Chem Lett. 2023 Apr 6;14(13):3216-3221. doi: 10.1021/acs.jpclett.3c00238. Epub 2023 Mar 27.

Authors

Wentao Fan^{1

2

3}, Nan Yan^{1

3}, Jun Zha^{1

2

3}, Wanmiao Gu^{1

3}, Qing You^{1

3}, Ying Yang^{1

3}, Shengli Zhuang^{1

3}, Zhikun Wu^{1

3}

Affiliations

¹ 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.
² University of Science and Technology of China, Hefei 230026, P. R. China.
³ Institute of Physical Science and Information Technology, Anhui University, Hefei, Anhui 230601, P. R. China.

PMID: 36971502
DOI: 10.1021/acs.jpclett.3c00238

Abstract

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: Au₂₈(SPh-^tBu)₁₈(SCH₂SCH₂S) and Au₂₈(SPh-^tBu)₁₈(SCH₂CH₂CH₂S). Both experimental and theoretical results demonstrated the regulation of the electronic structure (dipole moment) in the z (longitudinal) and x 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.