两个二亚胺-铜(Ⅰ)-膦配合物的合成、结构和太赫兹时域光谱（英文）  

Syntheses,Structures and Terahertz Time-Domain Spectroscopy of Two Diimine-Copper(Ⅰ)-Phosphine Complexes

作　　者：朱宁 潘迅 林森[1] 杨玉平[3] 辛秀兰 李中峰[1] 张帆[1] 金琼花[1,2] ZHU Ning;PAN Xun;LIN Sen;YANG Yu-Ping;XIN Xiu-Lan;LI Zhong-Feng;ZHANG Fan;JIN Qiong-Hua(Department of Chemistry,Capital Normal University,Beijing 100048,China;State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China;School of Science,Minzu University of China,Beijing 100081,China;School of Food and Chemical Engineering,Beijing Technology and Business University,Beijing 100048,China)

机构地区：[1]首都师范大学化学系,北京100048 [2]中国科学院福建物质结构研究所,结构化学国家重点实验室,福州350002 [3]中央民族大学理学院,北京100081 [4]北京工商大学食品学院,北京100048

出　　处：《无机化学学报》2020年第1期183-191,共9页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21171119,81573822,11574408,21671144);北京市自然科学基金(No.2172017,2172012)资助项目

摘　　要：本文报道了2个新的Cu(Ⅰ)配合物:[Cu(PPh3)2(dppz)]I(1)(PPh3=三苯基膦,dppz=二吡啶并[3,2-a∶2′,3′-c]吩嗪)和[Cu2(dppm)2(dppz)2]Cl2(2)(dppm=双(二苯基膦)甲烷)的合成,并通过X射线单晶衍射、元素分析、核磁共振氢(膦)谱、荧光光谱和太赫兹时域光谱对其进行了分析和表征。分析结果显示配合物1是一个单核配合物,中心Cu(Ⅰ)离子与2个含膦配体(PPh3)和1个含氮配体(dppz)进行配位,形成了一个扭曲的四面体结构。与1不同的是,配合物2是由CuCl,dppm和dppz以1∶1∶1的比例混配得到的双核配合物。其中,双膦配体dppm作为桥联配体,连接了2个Cu(Ⅰ)离子。荧光光谱表明所有的发射峰均源于金属到配体的电荷转移跃迁(MLCT)。同时,使用太赫兹时域光谱技术表征了2种配合物以及相应的配体。Herein,two novel copper(Ⅰ)complexes,[Cu(PPh3)2(dppz)]I(1)and[Cu2(dppm)2(dppz)2]Cl2(2)(PPh3=triphenylphosphine,dppz=dipyrido[3,2-a∶2′,3′-c]phenazine,dppm=bis(diphenylphosphino)methane)have been synthesized,and the characterization of the complexes was carried out through single-crystal X-ray diffraction,elemental analysis,IR,1H/31P NMR spectroscopy,fluorescence spectra and THz time domain spectroscopy(THz-TDS).The results show that 1 is a mononuclear complex.The central Cu(Ⅰ)builds a distorted tetrahedral geometry by coordinating with two phosphine ligands(PPh3)and one chelating N-donor ligand(dppz).Different from 1,2 exhibits a dinuclear structure which was obtained by the reaction of CuCl and dppm with dppz in 1∶1∶1 molar ratio,where the diphosphine ligand(dppm)was utilized as a bridging ligand coordinating to two copper(Ⅰ)atoms.The luminescent spectra show that the emission mechanism belongs to metal-to-ligand charge transfer(MLCT).At the same time,the terahertz(THz)time-domain spectroscopy was used to represent these two complexes as well as the corresponding ligands.CCDC:1558489,1;1915009,2.

关 键 词：铜(Ⅰ)配合物 结构 荧光 太赫兹时域光谱 二吡啶并[3 2-a∶2′ 3′-c]吩嗪 

分 类 号：O614.121[理学—无机化学]