氰基芳香羧酸配合物的合成、結(jié)構(gòu)和性能
發(fā)布時間：2018-08-03 16:52
【摘要】：芳香羧酸類配合物因其豐富多樣的結(jié)構(gòu),優(yōu)良的光、磁、電、催化等性能而成為廣大科學(xué)研究者關(guān)注的熱點(diǎn)。芳香羧酸配體的羧基存在著強(qiáng)的配位能力,豐富多樣的配位模式;稀土離子具有較高的配位數(shù),強(qiáng)的親氧特性以及優(yōu)良的發(fā)光和磁學(xué)性能,因此稀土離子可與芳香羧酸類配體配位形成結(jié)構(gòu)多樣、性能優(yōu)良的稀土配合物。配體4-氰基苯甲酸和5-氰基間苯二甲酸含有-COOH與-CN兩個配位能力有較大差異的功能性基團(tuán),存在離域的π電子共軛體系,光輻射下電子轉(zhuǎn)移行為豐富,有助于合成性能優(yōu)異的功能性配合物。本論文選取這2種氰基芳香羧酸作主配體,采用微波合成與揮發(fā)法相結(jié)合,通過調(diào)節(jié)反應(yīng)原料配比、體系pH、反應(yīng)時間、微波功率及反應(yīng)溫度等反應(yīng)條件,在溶液中與各種金屬離子成功組裝了9個稀土配合物和2個過渡金屬配合物。1.以4-氰基苯甲酸為配體,稀土離子為中心離子,通過微波法合成了7個同構(gòu)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))。測試了它們的紅外圖譜、X-射線粉末衍射圖譜、熱重曲線并進(jìn)行了相關(guān)分析。在室溫條件下測試了配合物1,3,4的固態(tài)激發(fā)和發(fā)射光譜,配合物1在268 nm的紫外光照射下發(fā)出了強(qiáng)的橙色光;配合物3在392 nm的激發(fā)波長下,發(fā)出了強(qiáng)的紅色光;配合物4在273 nm的紫外激發(fā)波長下發(fā)出了強(qiáng)的綠色特征光。利用發(fā)光性能探究了配合物3對部分金屬陽離子是否具有識別和檢測效應(yīng),實(shí)驗(yàn)發(fā)現(xiàn),配合物3對Zn2+、Fe2+、Fe3+等有著較靈敏的檢測效應(yīng)。2.以5-氰基間苯二甲酸為主配體,稀土Nd(III)離子、Sm(III)離子分別為中心離子,采用上述同樣的方法合成了兩個三維的稀土配合物[NdL3(H2O)5]·(HL3)·4H2O(8),[NH4]·[Sm L3(H2O)5]·(HL3)·2H2O(9)(L3=5-氰基間苯二甲酸),測試了它們的X-射線粉末衍射圖譜、紅外吸收圖譜、熱重曲線等進(jìn)行有關(guān)分析。配合物8能夠穩(wěn)定地存在于150℃-335℃溫度范圍內(nèi)。在室溫條件下測定了配合物9的固態(tài)發(fā)光光譜,其在279 nm的激發(fā)波長下發(fā)出了特征的橙色光。利用配合物9的發(fā)光特性研究了其對金屬陽離子的檢測效應(yīng),結(jié)果表明,配合物9的水溶液對Fe2+、Ag+、Fe3+等有識別作用。3.以4-氰基苯甲酸為配體,與過渡金屬鎘鹽、銅鹽分別反應(yīng)得到了兩例結(jié)構(gòu)新穎的配合物Cd3L16(HL1)6(H2O)2(10)和[Cu3L16(H2O)6]·(H2O)3(11)(L1=4-cba)。其中,配合物10的分子結(jié)構(gòu)為獨(dú)特的直線型三核結(jié)構(gòu),三核結(jié)構(gòu)經(jīng)分子間氫鍵作用連接,形成了一個二維層狀結(jié)構(gòu)。配合物11中包含了四種不同的銅原子,銅原子間經(jīng)雙齒4-氰基苯甲酸配體和兩個水分子的三橋聯(lián)作用形成了一個沿a軸方向的一維“之”字鏈。表征了這兩種配合物的IR、PXRD、TG等圖譜并進(jìn)行了分析。本論文采用微波合成與母液揮發(fā)相結(jié)合的方法得到了11個氰基苯甲酸配合物,合成方法有別于傳統(tǒng)的溶劑熱、水熱合成法,研究了部分配合物的發(fā)光性能及對金屬陽離子的檢測效應(yīng),為氰基苯甲酸稀土/過渡金屬配合物的合成及性質(zhì)研究提供了一些有參考價(jià)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.
【學(xué)位授予單位】：重慶師范大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O641.4
本文編號：2162377
[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.
【學(xué)位授予單位】：重慶師范大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O641.4
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