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Dithiol-Induced Contraction in Ag14 Clusters and Its Manifestation in Electronic Structures
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2020-09-28 , DOI: 10.1021/acs.jpcc.0c07140 Mohammad Bodiuzzaman 1 , Esma Khatun 1 , Korath Shivan Sugi 1 , Ganesan Paramasivam 1 , Wakeel Ahmed Dar 1 , Sudhadevi Antharjanam 2 , Thalappil Pradeep 1
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2020-09-28 , DOI: 10.1021/acs.jpcc.0c07140 Mohammad Bodiuzzaman 1 , Esma Khatun 1 , Korath Shivan Sugi 1 , Ganesan Paramasivam 1 , Wakeel Ahmed Dar 1 , Sudhadevi Antharjanam 2 , Thalappil Pradeep 1
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We report a dithiol-protected silver cluster, Ag14(BDT)6(PPh3)8 (BDT = 1,2-benzene dithiol), abbreviated as Ag14DT, which exhibits distinctly different optical properties than the analogous monothiol-protected Ag14(SC6H3F2)12(PPh3)8, abbreviated as Ag14MT. Replacement of monothiol by dithiol, keeping the composition constant, has not been possible so far. The inner cores of both Ag14DT and Ag14MT are composed of octahedral Ag6, but because of the presence of dithiol, the outer cubic Ag8 shell became distorted in the former. Consequently, Ag14DT showed a unique absorption in the near-infrared (NIR) region, which is mainly due to transitions derived from ligands. It exhibits dual visible/NIR emission, at around 680 and 997 nm. Ag14DT exhibited greater thermal stability because of the rigidity provided by dithiol ligands. The clusters with NIR absorption and emission open up a possibility for their application in solar thermal conversion and medical imaging. NIR luminescence in the range of 1000 nm in ultrasmall clusters is very new.
中文翻译：
Ag 14团簇中二硫醇诱导的收缩及其在电子结构中的表现
我们报告了二硫醇保护的银簇，Ag 14（BDT）6（PPh 3）8（BDT = 1,2-苯二硫醇），缩写为Ag 14 DT，与相似的单硫醇保护的Ag相比，它表现出明显不同的光学性质14（SC 6 H 3 F 2）12（PPh 3）8，缩写为Ag 14 MT。迄今为止，不可能通过二硫醇代替一硫醇以保持组成恒定。Ag 14 DT和Ag 14 MT的内芯均由八面体Ag 6组成，但由于存在二硫醇，外层立方Ag 8壳在前者中变形。因此，Ag 14 DT在近红外（NIR）区域显示出独特的吸收，这主要归因于源自配体的跃迁。它在680和997 nm处表现出双重可见/近红外发射。由于二硫醇配体提供的刚性，Ag 14 DT表现出更高的热稳定性。具有近红外吸收和发射的星团为它们在太阳热转换和医学成像中的应用打开了可能性。在超小型星团中1000 nm范围内的NIR发光是非常新的。
更新日期：2020-10-22
中文翻译：
Ag 14团簇中二硫醇诱导的收缩及其在电子结构中的表现
我们报告了二硫醇保护的银簇，Ag 14（BDT）6（PPh 3）8（BDT = 1,2-苯二硫醇），缩写为Ag 14 DT，与相似的单硫醇保护的Ag相比，它表现出明显不同的光学性质14（SC 6 H 3 F 2）12（PPh 3）8，缩写为Ag 14 MT。迄今为止，不可能通过二硫醇代替一硫醇以保持组成恒定。Ag 14 DT和Ag 14 MT的内芯均由八面体Ag 6组成，但由于存在二硫醇，外层立方Ag 8壳在前者中变形。因此，Ag 14 DT在近红外（NIR）区域显示出独特的吸收，这主要归因于源自配体的跃迁。它在680和997 nm处表现出双重可见/近红外发射。由于二硫醇配体提供的刚性，Ag 14 DT表现出更高的热稳定性。具有近红外吸收和发射的星团为它们在太阳热转换和医学成像中的应用打开了可能性。在超小型星团中1000 nm范围内的NIR发光是非常新的。
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