氰基芳香羧酸配合物的合成、结构和性能

发布时间：2018-08-03 16:52

【摘要】：芳香羧酸类配合物因其丰富多样的结构,优良的光、磁、电、催化等性能而成为广大科学研究者关注的热点。芳香羧酸配体的羧基存在着强的配位能力,丰富多样的配位模式;稀土离子具有较高的配位数,强的亲氧特性以及优良的发光和磁学性能,因此稀土离子可与芳香羧酸类配体配位形成结构多样、性能优良的稀土配合物。配体4-氰基苯甲酸和5-氰基间苯二甲酸含有-COOH与-CN两个配位能力有较大差异的功能性基团,存在离域的π电子共轭体系,光辐射下电子转移行为丰富,有助于合成性能优异的功能性配合物。本论文选取这2种氰基芳香羧酸作主配体,采用微波合成与挥发法相结合,通过调节反应原料配比、体系pH、反应时间、微波功率及反应温度等反应条件,在溶液中与各种金属离子成功组装了9个稀土配合物和2个过渡金属配合物。1.以4-氰基苯甲酸为配体,稀土离子为中心离子,通过微波法合成了7个同构的稀土配合物,即[NH4]2·[Ln(L1)5·(H2O)2]·(L2)0.5(L1=4-cba,L2=H2NCOC6H4CONH2,Ln=Sm(1)、Nd(2)、Eu(3)、Tb(4)、Dy(5)、Er(6)、La(7))。测试了它们的红外图谱、X-射线粉末衍射图谱、热重曲线并进行了相关分析。在室温条件下测试了配合物1,3,4的固态激发和发射光谱,配合物1在268 nm的紫外光照射下发出了强的橙色光;配合物3在392 nm的激发波长下,发出了强的红色光;配合物4在273 nm的紫外激发波长下发出了强的绿色特征光。利用发光性能探究了配合物3对部分金属阳离子是否具有识别和检测效应,实验发现,配合物3对Zn2+、Fe2+、Fe3+等有着较灵敏的检测效应。2.以5-氰基间苯二甲酸为主配体,稀土Nd(III)离子、Sm(III)离子分别为中心离子,采用上述同样的方法合成了两个三维的稀土配合物[NdL3(H2O)5]·(HL3)·4H2O(8),[NH4]·[Sm L3(H2O)5]·(HL3)·2H2O(9)(L3=5-氰基间苯二甲酸),测试了它们的X-射线粉末衍射图谱、红外吸收图谱、热重曲线等进行有关分析。配合物8能够稳定地存在于150℃-335℃温度范围内。在室温条件下测定了配合物9的固态发光光谱,其在279 nm的激发波长下发出了特征的橙色光。利用配合物9的发光特性研究了其对金属阳离子的检测效应,结果表明,配合物9的水溶液对Fe2+、Ag+、Fe3+等有识别作用。3.以4-氰基苯甲酸为配体,与过渡金属镉盐、铜盐分别反应得到了两例结构新颖的配合物Cd3L16(HL1)6(H2O)2(10)和[Cu3L16(H2O)6]·(H2O)3(11)(L1=4-cba)。其中,配合物10的分子结构为独特的直线型三核结构,三核结构经分子间氢键作用连接,形成了一个二维层状结构。配合物11中包含了四种不同的铜原子,铜原子间经双齿4-氰基苯甲酸配体和两个水分子的三桥联作用形成了一个沿a轴方向的一维“之”字链。表征了这两种配合物的IR、PXRD、TG等图谱并进行了分析。本论文采用微波合成与母液挥发相结合的方法得到了11个氰基苯甲酸配合物,合成方法有别于传统的溶剂热、水热合成法,研究了部分配合物的发光性能及对金属阳离子的检测效应,为氰基苯甲酸稀土/过渡金属配合物的合成及性质研究提供了一些有参考价值的方法。
[Abstract]:Aromatic carboxylic complexes have become the focus of scientific researchers because of their rich and diverse structures, excellent optical, magnetic, electrical and catalytic properties. The carboxyl carboxyl of aromatic carboxylic ligands has strong coordination ability, rich and diverse coordination modes; rare earth ions have high coordination numbers, strong oxygen properties and excellent luminescence and magnetism. As a result, rare earth ions can be coordinated with aromatic carboxylic ligands to form a complex structure and excellent rare earth complexes. The ligand 4- cyanbenzoic acid and 5- cyanyl benzene two formic acid contain functional groups with two different coordination abilities of -COOH and -CN, and there is a delocalized pion conjugated system, and the electron transfer behavior under light radiation is abundant. In this paper, these 2 kinds of Cyanoaromatic carboxylic acids are selected as the main ligands. The 2 kinds of Cyanoaromatic carboxylic acids are selected as the main ligands. The combination of microwave synthesis and volatilization is used. By adjusting the ratio of the reaction materials, the reaction time, the microwave power and the reaction temperature, 9 dilute materials are successfully assembled with various metal ions in the solution. Soil complexes and 2 transition metal complexes,.1. with 4- cyanbenzoic acid as ligands and rare earth ions as central ions, synthesized 7 isomorphic rare earth complexes by microwave method, namely, [NH4]2. [Ln (L1) 5. (H2O) 2]. (L2) 0.5 (L1=4-cba, L2=H2NCOC6H4CONH2, Ln=Sm (1), Nd (2), 3), 4, 6, 6, 7). The ray powder diffraction pattern, thermogravimetric curve and correlation analysis were carried out. The solid state excitation and emission spectra of the complex 1,3,4 were measured at room temperature. A strong orange light was emitted by the complex 1 under ultraviolet light of 268 nm; strong red light was emitted at the excitation wavelength of the complex 3 at 392 nm, and the complex 4 at 273 nm was excited by the UV wave. A strong green characteristic light was sent out. Using the luminescence properties, the recognition and detection effect of the complex 3 on the partial metal cations was investigated. It was found that the complex 3 had a more sensitive detection effect on Zn2+, Fe2+, Fe3+ and so on with 5- cyanoethyl two formic acid as the main ligand, the rare earth Nd (III) ion, and Sm (III) ion as the central separation, respectively. Two three dimensional rare earth complexes, [NdL3 (H2O) 5] (HL3), 4H2O (8), [NH4], [Sm L3 (H2O) 5]. (HL3) 2H2O (9) (9), were synthesized by the same method, and their X-ray powder diffraction patterns, infrared absorption spectra, thermogravimetric curves and so on were tested. The complex 8 can exist steadily in 150. In the temperature range of -335 C, the solid state luminescence spectra of the complex 9 were measured at room temperature. The orange light was emitted at the excitation wavelength of 279 nm. The detection effect of the metal cations on the metal cation was studied by the luminescence characteristics of the complex 9. The results showed that the aqueous solution of the complex 9 had a recognition effect on Fe2+, Ag+, Fe3+ and so on. Cyanbenzoic acid was used as a ligand to react with transition metal cadmium salt and copper salt to obtain two novel complexes Cd3L16 (HL1) 6 (H2O) 2 (10) and [Cu3L16 (H2O) 6]. (H2O) 3 (11) (L1=4-cba). Among them, the molecular structure of the complex 10 is a unique linear three nuclear structure, and the three nuclear structure is connected by intermolecular hydrogen bonding, forming a two dimension. Four different copper atoms are included in the complex. The copper atom is formed by the triple bridge of the double teeth 4- cyanbenzoic acid ligands and two water molecules. The IR, PXRD, TG, etc. of the two complexes are characterized and analyzed. The microwave synthesis and mother liquid are used in this paper. 11 cyanbenzoic acid complexes are obtained by the method of volatile phase binding. The synthesis method is different from the traditional solvothermal and hydrothermal synthesis methods. The luminescence properties of some complexes and the detection effect on the metal cations are studied. Some valuable references are provided for the study of the synthesis and properties of rare earth / transition metal complexes of cyanbenzoate. Method.
【学位授予单位】：重庆师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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