芳香多羧酸及氮杂环构筑的配位聚合物的合成、表征及性能研究
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摘要
配位聚合物由于在光、电、磁、催化、气体吸附等领域具有诱人的应用前景,已成为功能材料领域的研究热点之一。目前通过使用有机羧酸、咪唑和吡啶衍生物等各种有机配体,已经制备出大量的配合物。其中芳香多羧酸连接由于其变化多样的配位模式被认为是优秀的结构构筑器,并最多地应用于配合物的合成中。本文围绕配合物研究的热点问题,设计合成了三个新的有机芳香羧酸配体和九个配合物,并对他们的热稳定性和荧光性能进行了研究。
本论文主要包括以下三部分：
1.三种有机配体的合成：以对硝基苯酚、对叔丁基苯酚、对甲氧羰基苯硼酸等为原料,通过卤化、偶联、水解等反应合成了4-硝基-2,6-二(4-羧基苯基)苯酚(L1)和4-叔丁基-2,6-二(4-羧基苯基)苯酚(L2)；以尿素、乙酰丙酮、三氯氧磷、间甲氧羰基苯硼酸等为原料,通过取代、偶联、氧化等多步反应合成了2-(3-羧基苯基)-嘧啶-4,6-二羧酸(L3)；并通过1H NMR、13CNMR. IR、元素分析等对其进行了表征。
2.九个配位聚合物的合成：(1)以L3为配体,通过水热方法,分别与稀土硝酸盐Dy(NO3)3·6H2O、 Er(NO3)3·6H2O、 Ho(NO3)3·6H2O、 Tm(NO3)3·6H2O、 Tb(NO3)3·6H2O、 Sm(NO3)3·6H2O反应,构筑了六种稀土金属配位聚合物；(2)分别以L1、L3为主配体,1,4-二咪唑丁烷(bib)为辅配体,通过水热方法,与Cd(NO3)2·4H2O、 CdCl2·2.5H2O反应合成了两种过渡金属的配合物；(3)以4,4’-联苯二甲酸(L4)为配体,通过溶剂热方法,一定条件下与Cd(NO3)24H2O反应,合成了金属镉的配位聚合物[Cd(L4)(H2O)2]n。
3.配位聚合物的表征及性质研究：我们用单晶X-射线衍射、粉末衍射、元素分析、红外等对合成的配合物进行了表征；此外,对配合物1-5、8的热稳定性进行了分析,结果显示配合物8的热稳定性较好；通过荧光分析我们发现,只有配合物1、3、8能显示一定程度的荧光,其中配合物8的发光强度相对较好。
Due to the potential applications of coordination polymers in the fields of light, electricity, magnetism, catalysis, gas adsorption, etc., they have become one of the hot research realms in functional materials. So far, a large number of coordination polymers have been prepared by using various organic ligands, such as carboxylate acids, imidazoles, and pyridine derivatives. Because of the versatile coordination modes, aromatic carboxylate linkers are considered to be excellent structural constructors and most used to construct coordination polymers. Herein, based on the current research in the field of coordination chemistry, we designed and synthesized three novel aromatic polycarboxylate ligands and nine complexes through hydrothermal synthesis methods; furthermore, the thermal stabilities and photoluminescence of them were studied.
The main contents of this paper include the following three parts:
1. Synthesis of three organic ligands:4-Nitro-2,6-Bi(4-Carboxyphenyl)phenol(L1) and4-tert-Butyl-2,6-Bi(4-Carboxyphenyl)phenol(L2) were synthesized by coupling, hydrolysis and other multi-step reaction using4-Nitro-phenol,4-tert-Butyl-phenol and p-methoxycarbonylphenyl boronic acid as raw materials;2-(3-Carboxyphenyl)-pyrimidine-4,6-dicarboxylic acid(L3) was synthesized by substitution, coupling, oxidation and other multi-step reaction using acetylacetone, urea, m-methoxycarbonylphenyl boronic acid as raw materials. And their structures were determined by1H NMR,13C NMR, IR, elemental analysis.
2. Synthesis of nine coordination Polymers:(1)Six new lanthanide coordination polymers were synthesized via hydrothermal using ligand L3and rare earths metal salts Dy(NO3)3·6H2O, Er(NO3)3·6H2O、Ho(NO3)3·6H2O, Tm(NO3)3-6H2O、 Tb(NO3)3·6H2O、 Sm(NO3)3·6H2O.(2)Two new transition metal coordination polymers were synthesized via hydrothermal using L1, L3as the main ligand, 1,4-bimidazole butane(bib) as the second ligand and transition metal salts Cd(NO3)2·4H2O、 CdCl2-2.5H2O.(3)0ne new coordination polymers[Cd(L4)(H2O)2]n were synthesized via solvothermal using ligand L4and metal salts Cd(NO3)2-4H2O
3. Characterization and Property of coordination polymers:Polymers1-9were characterized by element analyses, IR spectroscopy, Powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. The thermal stabilities of polymers1-5、8were analyzed and the results showed that8has a better thermal stability. Moreover, we found that only complexes1,3and8can show a certain degree of fluorescence.
本论文主要包括以下三部分：
1.三种有机配体的合成：以对硝基苯酚、对叔丁基苯酚、对甲氧羰基苯硼酸等为原料,通过卤化、偶联、水解等反应合成了4-硝基-2,6-二(4-羧基苯基)苯酚(L1)和4-叔丁基-2,6-二(4-羧基苯基)苯酚(L2)；以尿素、乙酰丙酮、三氯氧磷、间甲氧羰基苯硼酸等为原料,通过取代、偶联、氧化等多步反应合成了2-(3-羧基苯基)-嘧啶-4,6-二羧酸(L3)；并通过1H NMR、13CNMR. IR、元素分析等对其进行了表征。
2.九个配位聚合物的合成：(1)以L3为配体,通过水热方法,分别与稀土硝酸盐Dy(NO3)3·6H2O、 Er(NO3)3·6H2O、 Ho(NO3)3·6H2O、 Tm(NO3)3·6H2O、 Tb(NO3)3·6H2O、 Sm(NO3)3·6H2O反应,构筑了六种稀土金属配位聚合物；(2)分别以L1、L3为主配体,1,4-二咪唑丁烷(bib)为辅配体,通过水热方法,与Cd(NO3)2·4H2O、 CdCl2·2.5H2O反应合成了两种过渡金属的配合物；(3)以4,4’-联苯二甲酸(L4)为配体,通过溶剂热方法,一定条件下与Cd(NO3)24H2O反应,合成了金属镉的配位聚合物[Cd(L4)(H2O)2]n。
3.配位聚合物的表征及性质研究：我们用单晶X-射线衍射、粉末衍射、元素分析、红外等对合成的配合物进行了表征；此外,对配合物1-5、8的热稳定性进行了分析,结果显示配合物8的热稳定性较好；通过荧光分析我们发现,只有配合物1、3、8能显示一定程度的荧光,其中配合物8的发光强度相对较好。
Due to the potential applications of coordination polymers in the fields of light, electricity, magnetism, catalysis, gas adsorption, etc., they have become one of the hot research realms in functional materials. So far, a large number of coordination polymers have been prepared by using various organic ligands, such as carboxylate acids, imidazoles, and pyridine derivatives. Because of the versatile coordination modes, aromatic carboxylate linkers are considered to be excellent structural constructors and most used to construct coordination polymers. Herein, based on the current research in the field of coordination chemistry, we designed and synthesized three novel aromatic polycarboxylate ligands and nine complexes through hydrothermal synthesis methods; furthermore, the thermal stabilities and photoluminescence of them were studied.
The main contents of this paper include the following three parts:
1. Synthesis of three organic ligands:4-Nitro-2,6-Bi(4-Carboxyphenyl)phenol(L1) and4-tert-Butyl-2,6-Bi(4-Carboxyphenyl)phenol(L2) were synthesized by coupling, hydrolysis and other multi-step reaction using4-Nitro-phenol,4-tert-Butyl-phenol and p-methoxycarbonylphenyl boronic acid as raw materials;2-(3-Carboxyphenyl)-pyrimidine-4,6-dicarboxylic acid(L3) was synthesized by substitution, coupling, oxidation and other multi-step reaction using acetylacetone, urea, m-methoxycarbonylphenyl boronic acid as raw materials. And their structures were determined by1H NMR,13C NMR, IR, elemental analysis.
2. Synthesis of nine coordination Polymers:(1)Six new lanthanide coordination polymers were synthesized via hydrothermal using ligand L3and rare earths metal salts Dy(NO3)3·6H2O, Er(NO3)3·6H2O、Ho(NO3)3·6H2O, Tm(NO3)3-6H2O、 Tb(NO3)3·6H2O、 Sm(NO3)3·6H2O.(2)Two new transition metal coordination polymers were synthesized via hydrothermal using L1, L3as the main ligand, 1,4-bimidazole butane(bib) as the second ligand and transition metal salts Cd(NO3)2·4H2O、 CdCl2-2.5H2O.(3)0ne new coordination polymers[Cd(L4)(H2O)2]n were synthesized via solvothermal using ligand L4and metal salts Cd(NO3)2-4H2O
3. Characterization and Property of coordination polymers:Polymers1-9were characterized by element analyses, IR spectroscopy, Powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. The thermal stabilities of polymers1-5、8were analyzed and the results showed that8has a better thermal stability. Moreover, we found that only complexes1,3and8can show a certain degree of fluorescence.
引文
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