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

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.