Luminescence in Functionalized Copper Thiolate Clusters – Synthesis and Structural Effects
Luminescence in Functionalized Copper Thiolate Clusters – Synthesis and Structural Effects
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DOI：
10.1002/ejic.201300155
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发表时间：
2013-07
影响因子：
2.3
通讯作者：
R. Langer;Munendra Yadav;B. Weinert;D. Fenske;O. Fuhr
中科院分区：
文献类型：
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作者：
R. Langer;Munendra Yadav;B. Weinert;D. Fenske;O. Fuhr
合成了一系列有机配体壳层含功能基的多核苯基硫醇铜（I）簇合物，并对其进行了单晶X射线衍射表征。描述了具有与苯基硫醇盐结合的Me2N基团的簇合物1 - 5，其具有不同的核性和核几何形状。的七核化合物6，其中包含苯硫醇和Me3SiO官能化的苯硫醇配体，是一个不寻常的混合硫醇盐簇的例子，并表现出几乎相同的核心5。从Cu···Cu原子间距较大的双核配合物到Cu···Cu原子间距较短的7个铜原子簇分子，这些化合物的光学性质都进行了研究。化合物1 - 5在500 nm以下显示出强吸收。强烈的发光覆盖可见光谱的宽范围（1：绿色; 2和3：蓝色; 4和5：黄色）。似乎光学跃迁发生在硫醇配体的轨道和金属中心轨道之间;对于具有短Cu···Cu距离的物种（3 - 5），这些相互作用导致光谱进一步红移。此外，官能团对光吸收和发射的影响由两个Cu7簇5和6示出，它们的区别仅在于它们的官能团的供电子性质。
A series of luminescent polynuclear copper(I) phenyl thiolate clusters with functional groups in the organic ligand shell has been synthesized and characterized by single-crystal X-ray diffraction. Cluster compounds 1–5 with Me2N groups bound to the phenyl thiolate are described and feature different nuclearities and core geometries. The heptanuclear compound 6, which contains both phenyl thiolate and Me3SiO functionalized phenyl thiolate ligands, is an unusual example of a mixed thiolate cluster and exhibits a core almost identical to that of 5. The optical properties of these compounds, which range from binuclear complexes with large Cu···Cu distances to cluster molecules with seven copper atoms and relatively short Cu···Cu distances, have been investigated. Compounds 1–5 show strong absorption below 500 nm. The intense luminescence covers a wide range of the visible spectrum (1: green; 2 and 3: blue; 4 and 5: yellow). It seems likely that the optical transitions occur between orbitals of the thiol ligands and metal-centered orbitals; for the species with short Cu···Cu distances (3–5), these interactions cause a further redshift of the spectra. In addition, the influence of functional groups on optical absorption and emission is shown by the two Cu7 clusters 5 and 6, which differ solely in the electron-donating nature of their functional groups.