Two novel Cu(Ⅰ)complexes based on diimide and bisphosphine ligands:synthesis,crystal structure and spectroscopic properties  

基于二亚胺和双膦配体的两种新型亚铜配合物的合成、晶体结构和光谱特性

作　　者：FAN Sijie ZHAO Jingtong ZHANG Shuai ZHANG Yuxin SUN Zhenzhou LI Zhongfeng HAN Hongliang XIN Xiulan JIN Qionghua 范思杰;赵婧彤;张帅;张钰鑫;孙振洲;李中峰;韩洪亮;辛秀兰;金琼花(首都师范大学化学系,北京100048;北京工商大学,轻工科学与工程学院,北京100048;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)

机构地区：[1]Department of Chemistry,Capital Normal University,Beijing 100048,China [2]School of Light Industry and Engineering,Beijing Technology and Business University,Beijing 100048,China [3]State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure,Chinese Academy of Sciences,Fuzhou 350002,China

出　　处：《黑龙江大学自然科学学报》2024年第5期526-535,共10页Journal of Natural Science of Heilongjiang University

基　　金：supported by the Key Project of Science and Technology Plan of Beijing Education Commission(KZ20231002808)。

摘　　要：Two Cu(Ⅰ)complexes[Cu(Bphen)(dppBz)]ClO_(4)·2CH_(3)OH(1)and[Cu_(2)(Bphen)_(2)(dpppda)]BF_(4)(2){Bphen=4,7-diphenyl-1,10-phenanthroline,dppBz=1,2-Bis(diphenylphosphino)benzene,dpppda=N1,N1,N4,N4-tetrakis[(diphenylphosphino)methyl]-1,4-benzenediamin}were synthesized using a one-pot method.X-ray crystallography was used to elucidate their crystal structures and photophysical properties.A series of characterization tests including elemental analysis,NMR,FT-IR,UV-Vis absorption spectroscopy,fluorescence spectroscopy,thermal gravimetric analysis and terahertz time-domain spectroscopy(THz-TDS)were used to further investigate their properties.The results show that complex 1 structure is mononuclear containing two solvent molecules per unit cell,while complex 2 structure is binuclear containing two metal centers per unit cell.According to photophysical properties and density functional theory(DFT)calculations,their luminescence properties can be attributed to metal-to-ligand charge transfer(MLCT).Both complexes have a unique stability,which is confirmed by thermal gravimetric analysis.采用一锅法合成了两种含有二亚胺和双膦配体的亚铜配合物,[Cu(Bphen)(dppBz)]ClO_(4)·2CH_(3)OH(1)和[Cu_(2)(Bphen)_(2)(dpppda)]BF_(4)(2){Bphen=4,7-二苯基-1,10-菲咯啉,dppBz=1,2-双(二苯基膦)苯,dpppda=N1,N1,N4,N4-四[(二苯基膦)甲基]-1,4-苯二胺}。使用X射线晶体学阐明了其晶体结构和光物理性质。通过元素分析、核磁共振、傅里叶变换红外光谱、紫外-可见吸收光谱、荧光光谱、热重分析和太赫兹时域光谱(Terahertz time-domain spectroscopy,THz-TDS)等一系列表征测试,进一步研究了其特性。结果表明,配合物1结构为单核结构,每个晶胞含有两个溶剂分子;配合物2结构为双核结构,每个晶胞含有两个金属原子中心。根据光物理性质和密度泛函理论(Density functional theory,DFT)的计算,它们的发光性质可归因于金属-配体电荷转移(Metal-to-ligand charge transfer,MLCT)。热重分析证实两种配合物都具有独特的稳定性。

关 键 词：Cu(Ⅰ)complex crystal structure fluorescence spectrum terahertz time-domain spectroscopy 

分 类 号：O641.4[理学—物理化学]