基于含氮衍生物和羧酸的Co(Ⅱ)配合物的合成、结构及磁学、荧光性质  

Synthesis,structure and magnetic and fluorescent properties of Co(Ⅱ)complexes based on nitrogen-containing derivatives and carboxylic acids

作　　者：赵越 刘宇奇[1] 金楠皓 王新颖[1] 刘小铭 陈寒 李玮[1,2] 李杨华 ZHAO Yue;LIU Yuqi;JIN Nanhao;WANG Xinying;LIU Xiaoming;CHEN Han;LI Wei;LI Yanghua(Faculty of Science,Kunming University of Science and Technology,Kunming 650500,Yunnan,China;Faculty of Metallurgical and Energy Engineering,Kunming University of Science and Technology,Kunming 650093,Yunnan,China)

机构地区：[1]昆明理工大学理学院,云南昆明650500 [2]昆明理工大学冶金与能源工程学院,云南昆明650093

出　　处：《云南大学学报（自然科学版）》2024年第2期309-318,共10页Journal of Yunnan University(Natural Sciences Edition)

基　　金：国家自然科学基金联合基金(u1502273);昆明理工大学分析测试基金(2021P20203102006,2021M20202111080)。

摘　　要：利用水热合成法合成了2种新型的金属有机配合物{[Co(Hbmp)_(2)(H_(2)O)·TFBDC}(1)和{[Co(Hbmp)(TDC)(H_(2)O)]}n(2)(Hbmp为2-(2-苯并咪唑基)-6-甲基吡啶,H2TFBDC为四氟对苯二甲酸,H2TDC为2,5-噻吩二甲酸),利用X射线单晶衍射、X射线粉末衍射、元素分析和红外光谱等方法对其结构进行表征.结果表明,配合物1的晶系是斜方晶系,Fddd空间群,中心离子Co(Ⅱ)为三角双锥构型,晶胞参数为a=1.47278(11)nm,b=2.9178(3)nm,c=3.0274(2)nm.配合物2的晶系是单斜晶系,C2/c空间群,中心离子Co(Ⅱ)为八面体构型,晶胞参数为a=1.77753(17)nm,b=1.84660(17)nm,c=1.33365(12)nm.零维结构的配合物1通过丰富的C—H…O、C—H…F、N-H…O、O—H…O氢键作用力形成三维超分子网状结构.配合物2则是利用羧酸的2种配位模式,将相邻的金属Co(Ⅱ)连接形成了一维链状结构,并借助于丰富的氢键作用力,也拓展成为了三维超分子的网状结构.利用紫外漫反射光谱分析,得到1的E_(g)值为2.65 eV,2的E_(g)值为2.85 eV,证明这2种配合物均是潜在的半导体材料.在1000 Oe的磁场作用下,在2~300 K之间研究了2个配合物的磁性,将测试的变温磁化率数据进行居里外斯拟合,得到居里外斯温度分别为-5.13 K和-5.84 K,证明了这2种配合物存在反铁磁相互作用.Two novel metal-organic complexes{[Co(Hbmp)_(2)(H_(2)O)]·TFBDC}(1),{[Co(Hbmp)(TDC)(H_(2)O)]}n(2)[Hbmp=2-(2-benzimidazolyl)-6-methylpyridine,H2TFBDC=tetrafluoroterephthalic acid,H2TDC=2,5-thiophene dicarboxylic acid]have been hydrothermally synthesized.Their structures were characterized by X-ray single crystal diffraction,X-ray powder diffraction,elemental analysis and infrared spectroscopy.The results showed that the crystal system of complex 1 is rhombohedral,Fddd space group,with the central ion Co(Ⅱ)in a triangular bipyramidal configuration and cell parameters of a=1.47278(11)nm,b=2.9178(3)nm and c=3.0274(2)nm.The crystal system of complex 2 is monoclinic,C2/c space group,with the central ion Co(Ⅱ)in an octahedral configuration and cellparameters of a=1.77753(17)nm,b=1.84660(17)nm,c=1.33365(12)nm.The zero-dimensional structure of complex 1 forms a three-dimensional supramolecular network through the rich hydrogen bonding forces of C—H···O,C—H···F,N—H···O,O—H···O.Complex 2 is a one-dimensional chain structure of the neighbouring metal Co(Ⅱ)using the two coordination modes of carboxylic acids,which is also expanded into a three-dimensional supramolecular mesh structure with the help of abundant hydrogen bonding forces.Using UV diffuse reflectance spectroscopy,an E_(g)value of 2.65 eV for 1 and 2.85 eV for 2 were obtained,demonstrating that both complexes are potential semiconductor materials.The magnetic property of the two complexes was also investigated at 2−300 K with an external magnetic field of 1000 Oe and magnetic susceptibility data were rationallyfitted with the Curie-Weiss Law at 2−300 K withθ=−5.13 K and−5.84 K,respectively,demonstrating the existence of antiferromagnetic interactions between the two complexes.

关 键 词：金属有机骨架化合物 水热合成 晶体结构 光学带隙 反铁磁性 

分 类 号：O611.4[理学—无机化学] O641[理学—化学] O743