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Regulating the Electronic Structure of Metal Nanoclusters by Longitudinal Single-Dithiolate Substitution
Wentao Fan1,2,3, Nan Yan1,3, Jun Zha1,2,3
1Key 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.
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-Bu)18(SCH2SCH2S) and Au28(SPh-Bu)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.
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