物理化学学报 >> 2018, Vol. 34 >> Issue (7): 776-780.doi: 10.3866/PKU.WHXB201711091

所属专题： 原子水平上精确控制纳米簇和纳米粒子

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夹心三明治结构的二十五核银硫簇合物[Ag25(SC6H4Pri)18 (dppp)6](CF3SO3)7·CH3CN：结构表征及光学性能

谢安1,王芝2,吴荞宇3,程丽萍2,3,骆耿耿3,*(),孙頔2,*()   

  1. 1 厦门理工学院材料科学与工程学院，福建省功能材料及应用重点实验室，福建 厦门 361024
    2 山东大学化学化工学院，胶体与界面化学教育部重点实验室，济南 250100
    3 华侨大学材料科学与工程学院，福建 厦门 361021
  • 收稿日期:2017-10-18 发布日期:2018-03-26
  • 通讯作者: 骆耿耿,孙頔 E-mail:ggluo@hqu.edu.cn;dsun@sdu.edu.cn
  • 基金资助:
    国家自然科学基金(21641011);国家自然科学基金(21571115);国家自然科学基金(21701133);福建省自然科学基金(2015J01053);福建省功能材料及应用重点实验室开放基金(fma2017107)

[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

An XIE1,Zhi WANG2,Qiaoyu WU3,Liping CHENG2,3,Genggeng LUO3,*(),Di SUN2,*()   

  1. 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
  • Received:2017-10-18 Published:2018-03-26
  • Contact: Genggeng LUO,Di SUN E-mail:ggluo@hqu.edu.cn;dsun@sdu.edu.cn
  • Supported by:
    the National Natural Science Foundation of China(21641011);the National Natural Science Foundation of China(21571115);the National Natural Science Foundation of China(21701133);the Natural Science Foundation of Fujian Province, China(2015J01053);the Fujian Key Laboratory of Functional Materials and Applications(fma2017107)

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摘要：

在本研究中，使用(iPrC6H4SAg)n作为合成银硫纳米簇合物的前驱体。当存在辅助的双膦配体1, 3-双(二苯基膦)丙烷(dppp)及可溶性银盐(CF3SO3Ag)，在超声合成条件下，获得了一例二十五核银硫簇合物Ag25，并借助X射线单晶衍射技术确定相应的分子结构。该银硫簇合物具有夹心三明治的骨架结构：分别由两个结构相似的圆柱体共享一个七核纯银簇所构成的金属簇平面。固态紫外可见漫反射光谱测试表明该簇合物的能级带隙为2.5 eV，属于半导体材料的范畴。固态发光测试显示，该簇合物在室温下发射绿光。

关键词: 银簇合物, 晶体结构, 光学性质, 发光性能, 银–银作用

Abstract:

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.

Key words: Silver cluster, Crystal structure, Optical property, Luminescence, Argentophilicity