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
赵越 1刘宇奇 1金楠皓 2王新颖 1刘小铭 1陈寒 1李玮 2李杨华1
作者信息
- 1. 昆明理工大学理学院,云南昆明 650500
- 2. 昆明理工大学理学院,云南昆明 650500;昆明理工大学冶金与能源工程学院,云南昆明 650093
- 折叠
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(H2O)]·TFBDC}(1)和{[Co(Hbmp)(TDC)(H2O)]}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Eg值为 2.65 eV,2 的Eg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.
Abstract
Two novel metal-organic complexes{[Co(Hbmp)2(H2O)]·TFBDC}(1),{[Co(Hbmp)(TDC)(H2O)]}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 Eg 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 with θ=-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Key words
MOFs/hydrothhermal synthesis/crystal structure/optical band gap/antiferromagnetism引用本文复制引用
基金项目
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)
昆明理工大学分析测试基金(2021M20202111080)
出版年
2024
NETL
NSTL
万方数据