由芳香羧酸构筑的系列Ni(Ⅱ)配合物的合成、结构及光电性能  

Synthesis,Structure and Photoelectric Property of A Series of Ni (Ⅱ) Complexes Constructed Through Aromatic Carboxylic Ligands

作　　者：贠吉星 胡志莉 李禹蒙[1] 金晶[1] 陈冲[1] 鄢欣[1] 刘永华[1] 丁榆[1] 迟玉贤[1] 牛淑云[1] YUN Jixing;HU Zhili;LI Yumeng;JIN Jing;CHEN Chong;YAN Xin;LIU Yonghua;DING Yu;CHI Yuxian;NIU Shuyun(School of Chemistry and Chemical Engineering,Liaoning Normal University,Dalian 116029,China)

机构地区：[1]辽宁师范大学化学化工学院,大连116029

出　　处：《高等学校化学学报》2018年第10期2161-2169,共9页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21133005);辽宁省自然科学基金(批准号:20170540576);辽宁省教育厅基金(批准号:L201783635)资助~~

摘　　要：采用水热法设计合成了6个基于芳香羧酸的Ni(Ⅱ)配合物:[Ni(pz)_4(H_2O)_2]·2H_2btc·H_2O(1),{[Ni_2(pz)_8(btec)]·4H_2O}n(2),{[Ni (H_2btec)(phen)]·2H_2O}n(3),[Ni (Hbdc)_2(pz)_4](4),{[Ni_3(bdc)_3(pz)_(12)]·2H_2O}n(5)和[Ni(bdc)(pz)_2(H_2O)]n(6)(pz=吡唑,H_3btc=1,3,5-苯三甲酸,H_4btec=1,2,4,5-苯四甲酸,phen=1,10-邻菲罗啉,H_2bdc=邻苯二甲酸).通过单晶X射线衍射、红外光谱(IR)、紫外-可见-近红外吸收光谱、元素分析、粉末X射线衍射(XRD)和表面光电压光谱(SPS)对其进行了结构和性质表征. 6个配合物的金属Ni(Ⅱ)中心呈五或六配位.配合物1和4具有完全由氢键网联成的2D超分子结构;配合物2和3是通过采取单齿/桥双齿配位模式的btec4-构筑的2D配位骨架结构;配合物5和6是由采取单齿/螯合双齿配位模式的bdc2-构筑的1D配位骨架结构,并由氢键连接成2D结构. 6个配合物在紫外和可见光诱导下均呈现出一定的光-电转换性能.当对配合物施加外加电场时,6个配合物的光电响应因配合物组成、结构键连方式以及配体种类的不同而呈现规律性变化.Six Ni(Ⅱ)complexes based on aromatic carboxylic ligands,[Ni(pz)4(H 2O)2]52H 2btc5H 2O(1),{[Ni 2(pz)8(btec)]54H 2O}n(2),{[Ni(H 2btec)(phen)]0x0E0xFF瘙0x01簚0x0F2H 2O}n(3),[Ni(Hbdc)2(pz)4](4),{[Ni 3(bdc)(pz)12]·2H 2O}n(5)and[Ni(bdc)(pz)2(H 2O)]n(6)(pz=pyrazole,H 3btc=1,3,5-benzenetricarbolylic acid,H 4btec=1,2,4,5-benzenetetracarboxylic acid,phen=1,10-phennanthroline,H 2bdc=1,2-benzenedicarboxylic acid),were hydrothermally synthesized.All the complexes were structurally and photophysically characterized by means of single crystal X-ray diffraction,infrared(IR)and UV-Vis-NIR electronic spectra,elemental analysis,X-ray diffraction(XRD)and surface photovoltage spectra(SPS).The Ni(Ⅱ)centers in six complexes have the square-pyramid or octahedral coordination environment.Complexes 1 and 4 have 2D supramolecular structure networked by hydrogen bonds.Complexes 2 and 3 possess 2D coordination framework structure constructed by btec 4-ligands with monodentate and monoatomic bridging modes.Complexes 5 and 6 have 1D coordination chain structure built by bdc 2-anions with monodentate/chelating coordination modes,which are further networked into 2D supramolecules by hydrogen bonds.All the six complexes exhibit certain photo-electric conversion properties under the inducement of UV-Vis lights.When a positive electric field is applied to the six complexes,the intensity change of photoelectric response of the six complexes presents difference which correlates with the bonding mode of the structure and type of the organic ligands.

关 键 词：芳香羧酸 Ni(Ⅱ)配合物 晶体结构 光物理性质 光电性能 

分 类 号：O614[理学—无机化学]