Citation: XIE An, WANG Zhi, WU Qiaoyu, CHENG Liping, LUO Genggeng, SUN Di. [Ag₂₅(SC₆H₄Prⁱ)₁₈(dppp)₆](CF₃SO₃)₇·CH₃CN (HSC₆H₄Prⁱ = 4-t-isopropylthiophenol, and dppp = 1, 3-bis(diphenyphosphino)propane) Cluster Containing a Sandwich-like Skeleton: Structural Characterization and Optical Properties[J]. Acta Physico-Chimica Sinica, ;2018, 34(7): 776-780. doi: 10.3866/PKU.WHXB201711091 shu

[Ag₂₅(SC₆H₄Prⁱ)₁₈(dppp)₆](CF₃SO₃)₇·CH₃CN (HSC₆H₄Prⁱ = 4-t-isopropylthiophenol, and dppp = 1, 3-bis(diphenyphosphino)propane) Cluster Containing a Sandwich-like Skeleton: Structural Characterization and Optical Properties

XIE An ^1,† ,
WANG Zhi ^2,† ,
WU Qiaoyu ³ ,
CHENG Liping ^2,3 ,
LUO Genggeng ^3,, ,
SUN Di ^2,,

1.
Key Laboratory of Functional Materials and Applications of Fujian Province, School of Materials Science and Engineering, Xiamen University of Technology, Xiamen 361024, Fujian Province, P. R. China
2.
Key Lab of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, P. R. China
3.
College of Materials Science and Engineering, Huaqiao University, Xiamen 361021, Fujian Province, P. R. China

Corresponding author: LUO Genggeng, ggluo@hqu.edu.cn SUN Di, dsun@sdu.edu.cn

^†

Received Date: 18 October 2017
Revised Date: 7 November 2017
Accepted Date: 8 November 2017
Available Online: 9 July 2017
Fund Project: the Fujian Key Laboratory of Functional Materials and Applications fma2017107the National Natural Science Foundation of China 21641011the National Natural Science Foundation of China 21571115the National Natural Science Foundation of China 21701133The project was supported by the National Natural Science Foundation of China (21641011, 21571115, 21701133), the Natural Science Foundation of Fujian Province, China (2015J01053) and the Fujian Key Laboratory of Functional Materials and Applications (fma2017107)the Natural Science Foundation of Fujian Province, China 2015J01053

Crystalline silver cluster compounds are highly interesting owing to their intriguing structure and potential technological application in luminescence, semiconductivity, and as precursors for nonlinear optical materials. Typically, the synthesis of silver clusters involves the use of protecting ligands such as thiolates, phosphines, and alkynes, which have been found to be critical for cluster size and shape tuning. Among these nanoclusters, pentacosanuclear silver clusters (Ag₂₅) have only been reported with either thiolate ligands or phosphine ligands, while those bearing mixed protecting ligands are rather rare. In the course of our exploration of novel silver clusters, a new silver thiolate precursor (ⁱPrC₆H₄SAg)_n was used to construct nanosized silver clusters. In the presence of 1, 3-bis(diphenyphosphino)propane (dppp) and CF₃SO₃Ag, the pentacosanuclear silver cluster [Ag₂₅(SC₆H₄Prⁱ)₁₈(dppp)₆](CF₃SO₃)₇·CH₃CN (designated as Ag₂₅, HSC₆H₄Prⁱ = 4-t-isopropylthiophenol) ligated both by thiolate and phosphine ligands was obtained under ultrasonic reaction conditions. Yellow block crystals were isolated from the solution, whose molecular structure was elucidated by single-crystal X-ray analysis. The skeleton of the Ag₂₅ cluster comprises a sandwich-like motif containing two structurally very similar cylinders sharing a metal-cluster plane. The core of each cylinder presents the overall shape of a twisted hexagonal cylinder made of two connected Ag₃S₃ units, with six sulfur atoms and six silver atoms alternating on a puckered drum-like surface. The metal-cluster plane contains one type of pure-Ag tetragons showing significant Ag…Ag argentophilic interactions. The optical properties of Ag₂₅ were investigated in the solid state. A band gap of ~2.5 eV was estimated for Ag₂₅ from the optical absorption spectrum, suggesting this cluster to be a potential wide-gap semiconductor. This Ag₂₅ cluster was also found to emit green luminescence at λ = 505 nm and room temperature.
- Silver cluster,
- Crystal structure,
- Optical property,
- Luminescence,
- Argentophilicity
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通讯作者: 陈斌, bchen63@163.com

[Ag₂₅(SC₆H₄Prⁱ)₁₈(dppp)₆](CF₃SO₃)₇·CH₃CN (HSC₆H₄Prⁱ = 4-t-isopropylthiophenol, and dppp = 1, 3-bis(diphenyphosphino)propane) Cluster Containing a Sandwich-like Skeleton: Structural Characterization and Optical Properties