两个二亚胺及双膦配体混配铜(Ⅰ)配合物的合成、结构与太赫兹光谱  

Syntheses,Crystal Structures and Terahertz Spectra of Two Copper(Ⅰ)Complexes Based on Mixed Diimines and Diphosphine Ligands

作　　者：孙振洲 孙凌志 朱宁 匡晓楠 杨玉平[3] 李中峰[1] 金琼花[1,2] 张江威 SUN Zhen-Zhou;SUN Ling-Zhi;ZHU Ning;KUANG Xiao-Nan;YANG Yu-Ping;LI Zhong-Feng;JIN Qiong-Hua;ZHANG Jiang-Wei(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;Dalian National Laboratory for Clean Energy&State Key Laboratory of Catalysis,Dalian Institute of Chemical Physics,Chinese Academy of Sciences(CAS),Dalian,Liaoning 116023,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]洁净能源国家实验室&催化基础国家重点实验室,中国科学院大连化学物理研究所,大连116023

出　　处：《无机化学学报》2020年第12期2261-2270,共10页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21171119,81573822,11574408,21671144,21701168);北京市自然科学基金(No.2172017,2172012);辽宁省自然科学基金(No.20180510050)资助项目。

摘　　要：在甲醇和二氯甲烷混合溶液中制备了2个二亚胺、双膦配体混配的铜(Ⅰ)配合物[Cu2(Dpq)2(dppBz)2](SCN)2·0.5Dpq·3CH3OH (1)和[Cu2(Dppz)2(dppb)2](BF4)2·2CH3OH·2H2O (2)(Dppz=二吡啶[3,2-a:2’,3’-c]并吩嗪,Dpq=吡嗪并[2,3-f][1,10]菲咯啉,dppBz=1,2-双(二苯基磷基)苯,dppb=1,4-双(二苯膦基)丁烷),通过X射线单晶衍射确定了配合物的精确结构,并使用元素分析、核磁共振氢谱、红外光谱、紫外可见吸收光谱、荧光光谱、太赫兹时域光谱(THz-TDS)对配合物进行了表征。1的晶胞中包含2个独立的金属中心,还含有0.5个未配位的Dpq分子,类似结构较为少见;而2为通过双膦配体桥联形成新颖的双核结构。通过弱相互作用力分析可知1为三维立体堆积结构,结构中含有独特的C-S…π作用;2通过C-H…π及π…π作用形成一维无限链,大量弱相互作用的存在使配合物更加稳定。发射光谱表明配合物1在578 nm处有较强的发射,而2在547 nm有绿光发射。配合物2的THz-TDS图中在1.2 THz处的尖锐峰是由C-H···F弱相互作用引起的。Two copper(Ⅰ) complexes with diimine and diphosphine ligands,[Cu2(Dpq)2(dppBz)2](SCN)2·0.5 Dpq·3CH3OH(1) and [Cu2(Dppz)2(dppb)2](BF4)2·2CH3OH·2H2O(2)(Dppz=dipyrido[3,2-a:2’,3’-c]phenazine,Dpq=pyrazino[2,3-f][1,10]phenanthroline,dppBz=1,2-bis(diphenylphosphino)benzene,dppb=1,3-bis(diphenylphosphine)butane),were prepared in the mixed solution of methanol and dichloromethane.The structure of these two complexes were determined by X-ray single crystal diffraction and characterized by elemental analysis,NMR,FT-IR,UV-Vis absorption spectrum,fluorescence spectrum and terahertz time-domain spectroscopy(THz-TDS).The unit cell of 1 contains two independent metal centers and half uncoordinated Dpq molecule,and similar structures are very rare.However,complex 2 are novel binuclear structure formed by the bisphosphine ligand.Through the analysis of intermolecular forces,1 is a three-dimensional stacked structure,which contains unique C-S…π interactions.But 2 forms one-dimensional infinite chain through C-H…πand π…π.The existence of a large number of weak interactions makes the complexes more stable.The emission spectra showed that the peak of complex 1 was at 578 nm,however,complex 2 emitted green light(at 547 nm).The sharp peak at 1.2 THz in THz-TDS spectrum of complex 2 is caused by the interactions of C-H…F.CCDC:1991845,1;1991844,2.

关 键 词：铜(Ⅰ)配合物 荧光 分子间作用力 太赫兹时域光谱 

分 类 号：O614.121[理学—无机化学]