基于双膦配体、氮配体的两个铜(Ⅰ)配合物的合成、光谱学性质和太赫兹时域光谱 |
Syntheses, Spectroscopic Properties and Terahertz Time Domain Spectroscopy of Two Copper(Ⅰ) Complexes Based on Diphosphine Ligands and N-Donor Ligands |
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摘要: 在甲醇和二氯甲烷的混合溶剂中合成了2个新的铜(Ⅰ)配合物:[Cu(dppp)(Bphen)]Cl·1.8CH3OH(1)和[Cu2(CN)2(dppp)(dmp)2]·2.5CH3OH(2)(dppp=1,3-双(二苯基膦基)丙烷,Bphen=4,7-二苯基-1,10-菲咯啉,dmp=2,9-二甲基-1,10-菲咯啉),并通过X射线单晶衍射、元素分析、红外光谱、核磁共振氢谱及磷谱、荧光光谱和太赫兹时域光谱对2个配合物进行了分析和表征。单晶结构表明配合物1是以Cu(Ⅰ)为中心,Bphen和dppp为配体,螯合形成的扭曲四面体结构。配合物2则是由CuCN、dppp和dmp以2:1:2的比例混合得到。配合物2的双膦配体的2个膦基分别与2个Cu(Ⅰ)形成配位键,每个Cu(Ⅰ)又分别与1个氰根和1个dmp配位。发光光谱表明配合物1和2所有的发射峰来源于金属-配体电荷迁移(MLCT)。太赫兹时域光谱对配合物1和2的研究提供了帮助。 |
关键词: 铜(Ⅰ)配合物 二亚胺 双膦 荧光光谱 太赫兹技术 |
基金项目: 国家自然科学基金(No.21171119,11574408,1376008)和北京市自然科学基金(No.2172017)资助。 |
Abstract: Two novel Cu(Ⅰ) complexes,[Cu(dppp) (Bphen)]Cl·1.8CH3OH (1) and[Cu2(CN)2(dppp)(dmp)2]·2.5CH3OH(2) (dppp=1,3-bis(diphenylphosphanyl) propane, Bphen=4,7-diphenyl-1,10-diazaphenanthrene, dmp=2,9-dimethyl-1, 10-phenanthroline), have been synthesized in a mixture of CH3OH and CH2Cl2 and characterized by single-crystal X-ray diffraction, elemental analysis, IR, 1H NMR and 31P NMR spectroscopy, fluorescence spectra and terahertz time-domain spectroscopy (THz-TDS). The single crystal X-ray diffraction shows that complex 1 is a distorted tetrahedral structure with copper as the center, Bphen and dppp as the chelating ligands. Complex 2 is obtained by mixing CuCN, dppp and dmp in a ratio of 2:1:2. The two phosphates of complex 2 form coordination bonds with two Cu(Ⅰ), and each copper coordinates with a cyanogen and a dmp, respectively. The luminescent spectra show that the emission mechanism of complexes 1 and 2 are metal-to-ligand charge transfer (MLCT). The application of THz-TDS also supports to the study of both the complexes. |
Keywords: copper(Ⅰ) complex diimine diphosphine luminescent spectra terahertz technology |
投稿时间:2021-03-21 修订日期:2021-06-25 |
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李紫曦,胡聪,孙振洲,李晓奇,韩洪亮,杨玉平,辛秀兰,金琼花.基于双膦配体、氮配体的两个铜(Ⅰ)配合物的合成、光谱学性质和太赫兹时域光谱[J].无机化学学报,2021,37(8):1504-1512. |
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