含刚性羧酸配体配合物的结构和性质
发布时间：2018-08-28 15:05
【摘要】：配位聚合物具有新颖的结构、独特的性质,在发光、吸附分离、气体储存和非均相催化等许多领域的有着潜在的应用价值,引起当代化学家的兴趣,成为当代化学研究中的热点领域之一。但是,合成具有特定拓扑结构的配位聚合物需要选取合适的配体、金属中心和在特定的合成途径下才可以得到,因此配位聚合物的设计和构筑仍是当前该领域的研究难点所在。羧酸类配体由于羧基氧可以提供多元化的配位方式和较强的配位键,一直以来被广泛用于合成配位聚合物。而其中带有苯环的羧酸配体具有刚性,更容易获得带有孔道的框架结构稳定的金属有机框架材料,因此是近些年来被研究最多的配体之一。但是现在单一的配体越发不能满足我们对于配合物结构精确把握的要求,因此一系列混合的配体被应用于同一反应体系。通过不同长度的连接体和多元化的配位方式,一类具有规律性的配位聚合物被成功合成出来,更为重要的是我们研究发现定量的辅助羧酸配体的存在可以起到准确酸度调节的作用,有助于结构新颖配位聚合物的合成。基于以上分析,本论文选择2,6-吡啶二羧酸(2,6-H2PDC)和2,5-二溴对苯二甲酸(2,5-H2Br2BDC)作为主羧酸配体,选择3,5-吡啶二羧酸(3,5-H2PDC)、2-羟基丙酸(Lac)和溴乙酸(BrMA)作为辅助羧酸配体,两两混合后再分别与单一金属或混合金属反应合成了十一种结构新颖的配位聚合物,并对其结构和性质进行了研究。本论文主要包括以下两个方面的工作:1、使用混合羧酸配体2,6-H2PDC和3,5-H2PDC与三组不同的双组份金属盐反应合成了一个单金属配位聚合物[Zn2(2,6-PDC)2] (1)和两个混金配位聚合物[CaPb6(2,6-PDC)6]C12 (2)和[Mg1.5Ce(2,6-PDC)3(H20)3]·3.5H20 (3)。三个配合物共同的特点是均只含有单一羧酸配体2,6-H2PDC。上述的配合物中尽管配体3,5-H2PDC没有参与反应,但是起到了酸度调节剂的作用。配合物另一重要的特点是其结构均可视为由金属-连接体次级构建单元和金属节点组成。配合物1具有sqI网络结构,可视为由两种不同的(4,4)拓扑结构的网络构成。一种二维网络是由压扁的四面体节点[Zn(2,6-PDC)2]2-金属-连接体次级构建单元和共享的五配位的Zn(Ⅱ)节点构成;另一种网络是由二联的2,6-PDC配体和四联的Zn(Ⅱ)节点组成。配合物2是由18-联的八面体[Ca(2,6-PDC)6]10-次级构建单元和三联的Pb(II)节点构成,形成了一个双节点的3, 18-联的gez网络。配合物3具有非常著名的4, 6-联的stp网络和一维三维1六角形纳米孔道,它可视为由6-联的三棱柱[Ce(2,6-PDC)3]3-金属-连接体次级构建单元和4-联的Mg(II)构成。此外,我们对配位聚合物1-3的热稳定性和固体荧光进行了测试。基于配位聚合物3的纳米孔道性质,我们考查了其对于碘分子的吸附和解吸性质。研究发现每个分子单元能吸附约0.28 12,增重8.9%。但是,吸附碘分子以后,配位聚合物3的解析性能不好。2、使用刚性棒状羧酸主配体2,5-H2Br2BDC和Lac、BrMA和3,5-H2PDC三种辅助羧酸配体与碱土金属Ca、Ba,过渡金属Fe、Zn,稀土金属La、Eu和主族金属Pb反应,通过溶剂热和常温挥发的方法得到了八个配位聚合物。其中八个配位聚合物中只含有2,5-H2Br2BDC,这一结果表明三种辅助羧酸配体可能也只起到了条件调节pH值得作用。使用乳酸作为辅助羧酸配体,得到了四个配合物[Zn(Br2BDC)(DMF)] (4) 、 [Fe2(Br2BDC)2(DMF)3] (5)、[Ba(Br2BDC)(DMF)(H20)] (6)、[Pb(Br2BDC)(DMF)] (7)。配合物 4 是由梯形链在平行的ab面内以…ABAB…的排列方式形成的二维网状结构。配合物5是由一维的方形孔道和41螺旋链通过共享金属节点构成的具有三种类型孔道的三维框架结构。配合物6是一种具有pcu拓扑的三维金属有机框架结构。配合物7是由砖墙型二维网通过Br2BDC配体作为支柱构成的三维框架结构。使用溴乙酸作为辅助配体,得到了三个配体物[Ba2(HBr2BDC)2(Br2BDC)(DMF)2(H2O)2] (8)、[La2(Br2BDC)3(DMF)4(H2O)2] (9)和[Eu2(Br2BDC)3(DMF)2(H2O)2]·2DMF (10)。配位8是一种沿a轴方向有两种一维孔道的三维框架结构。配位9和10的结构是类似的,都是由双核金属作为节点沿着b轴方向存在一维孔道的金属有机框架。使用刚性3,5-吡啶二甲酸作为辅助配体只得到了配合物[Ca2(Br2BDC)2(DMF)2(H2O)2](11)。配合物11的结构是一种两重的自互穿的nbo型的三维框架结构。上述结果表明Br2BDC配体的多样桥联模式有助于结构多样配合物的构建。
[Abstract]:Coordination polymers have novel structures, unique properties and potential applications in many fields, such as luminescence, adsorption separation, gas storage and heterogeneous catalysis. They have attracted the interest of modern chemists and become one of the hotspots in contemporary chemical research. However, the synthesis of coordination polymers with specific topological structures needs to be selected. Suitable ligands, metal centers, and specific synthetic routes are available. Therefore, the design and construction of coordination polymers are still difficult in this field. Carboxylic acid ligands have been widely used in the synthesis of coordination polymers because of their various coordination modes and strong coordination bonds provided by carboxyl oxygen. Carboxylic acid ligands with phenyl rings in them are rigid and easy to obtain stable metal-organic frameworks with porous structures, so they are one of the most studied ligands in recent years. However, single ligands are increasingly unable to meet our requirements for accurate grasp of the structure of the complexes, so a series of mixed ligands are prepared. Apply to the same reaction system. Through different lengths of ligands and diversified coordination methods, a kind of coordination polymers with regularity are successfully synthesized. More importantly, we found that the existence of quantitative auxiliary carboxylic acid ligands can play an accurate acidity regulation role, which is conducive to novel coordination polymers. Based on the above analysis, 2,6-pyridine dicarboxylic acid (2,6-H2PDC) and 2,5-dibromoterephthalic acid (2,5-H2Br2BDC) were selected as the main carboxylic acid ligands, 3,5-pyridine dicarboxylic acid (3,5-H2PDC), 2-hydroxypropionic acid (Lac) and bromoacetic acid (BrMA) were selected as auxiliary carboxylic acid ligands, and then mixed with a single metal or mixed metal respectively. Eleven novel coordination polymers have been synthesized and their structures and properties have been studied. The main work of this paper is as follows: 1. A single metal coordination polymer [Zn2 (2,6-PDC) 2] (1) and two mixed gold have been synthesized by the reaction of mixed carboxylic acid ligands 2,6-H2PDC and 3,5-H2PDC with three different groups of two-component metal salts. The coordination polymers [CaPb6(2,6-PDC)6] C12(2) and [Mg1.5Ce(2,6-PDC)3(H20)3].3.5H20(3). The common feature of the three complexes is that they all contain only a single carboxylic acid ligand 2,6-H2PDC. Although the ligands 3,5-H2PDC do not participate in the reaction, they act as acidity regulators. Another important characteristic of the complexes is that they all have structures. Complex 1 has a sqI network structure and can be viewed as a network of two different (4,4) topologies. A two-dimensional network consists of flattened tetrahedral nodes [Zn(2,6-PDC)2] 2-metal-connector secondary construction units and shared five-coordinated Zn(II) nodes. Complex 2 is composed of 18-linked octahedron [Ca(2,6-PDC)6] 10-secondary construction unit and three-linked Pb(II) nodes, forming a two-node 3,18-linked Gez network. Complex 3 has a very famous 4,6-linked STP network and one-dimensional three-dimensional one-hexahexahedron network. In addition, we tested the thermal stability and solid fluorescence of the coordination polymer 1-3. Based on the properties of the nanochannels of the coordination polymer 3, we examined its adsorption and dissolution of iodine molecules. Absorption properties. It was found that each molecular unit could absorb about 0.2812, with an increase of 8.9%. However, after the adsorption of iodine molecule, the analytical performance of coordination polymer 3 was poor. 2. Three auxiliary carboxylic acid ligands, 2,5-H2Br2BDC and Lac, BrMA and 3,5-H2PDC, were used to assist the carboxylic acid ligands with alkaline earth metals Ca, Ba, transition metal Fe, Zn, rare earth metals La, Eu and main group. Eight coordination polymers were synthesized by solvothermal and ambient temperature evaporation of metal Pb. Only 2,5-H2Br2BDC was found in eight of the coordination polymers. The results show that the three auxiliary carboxylic acid ligands may also play a role in conditioning pH. Four complexes [Zn (Br2BDC) were obtained by using lactic acid as auxiliary carboxylic acid ligand. (DMF)] (4, [Fe2 (Br2BDC) 2 (DMF) 3] (5), [Ba (Br2BDC) (DMF) (H20)] (6), [Pb (Br2BDC) (DMF)] (7). Complex 4 consists of a trapezoidal chain in a parallel ab plane with a uuuuuuuuuuu ABAB... Complex 5 is a three-dimensional framework consisting of one-dimensional square channels and 41 helical chains through shared metal nodes. Complex 6 is a three-dimensional metal-organic framework with a PCU topology. Complex 7 is a brick-wall two-dimensional network through a Br2BDC ligand. Three ligands [Ba2 (HBr2BDC) 2 (Br2BDC) (DMF) 2 (H2O) 2] (8), [La2 (Br2BDC) 3 (DMF) 4 (H2O) 2] (9) and [Eu2 (Br2BDC) 3 (DMF) 2 (H2O) 2 (10)] were obtained by using bromoacetic acid as an auxiliary ligand. Similarly, all of the metal-organic frameworks with one-dimensional channels along the b-axis are composed of Binuclear metals. Only the complex [Ca2 (Br2BDC) 2 (DMF) 2 (H2O) 2] (11) was obtained by using a rigid 3,5-pyridinedicarboxylic acid as an auxiliary ligand. The structure of complex 11 is a double self-penetrating nbo-like three-dimensional framework. The diverse bridging patterns of BDC ligands contribute to the construction of diverse structural complexes.
【学位授予单位】：山东科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4
本文编号：2209744
[Abstract]:Coordination polymers have novel structures, unique properties and potential applications in many fields, such as luminescence, adsorption separation, gas storage and heterogeneous catalysis. They have attracted the interest of modern chemists and become one of the hotspots in contemporary chemical research. However, the synthesis of coordination polymers with specific topological structures needs to be selected. Suitable ligands, metal centers, and specific synthetic routes are available. Therefore, the design and construction of coordination polymers are still difficult in this field. Carboxylic acid ligands have been widely used in the synthesis of coordination polymers because of their various coordination modes and strong coordination bonds provided by carboxyl oxygen. Carboxylic acid ligands with phenyl rings in them are rigid and easy to obtain stable metal-organic frameworks with porous structures, so they are one of the most studied ligands in recent years. However, single ligands are increasingly unable to meet our requirements for accurate grasp of the structure of the complexes, so a series of mixed ligands are prepared. Apply to the same reaction system. Through different lengths of ligands and diversified coordination methods, a kind of coordination polymers with regularity are successfully synthesized. More importantly, we found that the existence of quantitative auxiliary carboxylic acid ligands can play an accurate acidity regulation role, which is conducive to novel coordination polymers. Based on the above analysis, 2,6-pyridine dicarboxylic acid (2,6-H2PDC) and 2,5-dibromoterephthalic acid (2,5-H2Br2BDC) were selected as the main carboxylic acid ligands, 3,5-pyridine dicarboxylic acid (3,5-H2PDC), 2-hydroxypropionic acid (Lac) and bromoacetic acid (BrMA) were selected as auxiliary carboxylic acid ligands, and then mixed with a single metal or mixed metal respectively. Eleven novel coordination polymers have been synthesized and their structures and properties have been studied. The main work of this paper is as follows: 1. A single metal coordination polymer [Zn2 (2,6-PDC) 2] (1) and two mixed gold have been synthesized by the reaction of mixed carboxylic acid ligands 2,6-H2PDC and 3,5-H2PDC with three different groups of two-component metal salts. The coordination polymers [CaPb6(2,6-PDC)6] C12(2) and [Mg1.5Ce(2,6-PDC)3(H20)3].3.5H20(3). The common feature of the three complexes is that they all contain only a single carboxylic acid ligand 2,6-H2PDC. Although the ligands 3,5-H2PDC do not participate in the reaction, they act as acidity regulators. Another important characteristic of the complexes is that they all have structures. Complex 1 has a sqI network structure and can be viewed as a network of two different (4,4) topologies. A two-dimensional network consists of flattened tetrahedral nodes [Zn(2,6-PDC)2] 2-metal-connector secondary construction units and shared five-coordinated Zn(II) nodes. Complex 2 is composed of 18-linked octahedron [Ca(2,6-PDC)6] 10-secondary construction unit and three-linked Pb(II) nodes, forming a two-node 3,18-linked Gez network. Complex 3 has a very famous 4,6-linked STP network and one-dimensional three-dimensional one-hexahexahedron network. In addition, we tested the thermal stability and solid fluorescence of the coordination polymer 1-3. Based on the properties of the nanochannels of the coordination polymer 3, we examined its adsorption and dissolution of iodine molecules. Absorption properties. It was found that each molecular unit could absorb about 0.2812, with an increase of 8.9%. However, after the adsorption of iodine molecule, the analytical performance of coordination polymer 3 was poor. 2. Three auxiliary carboxylic acid ligands, 2,5-H2Br2BDC and Lac, BrMA and 3,5-H2PDC, were used to assist the carboxylic acid ligands with alkaline earth metals Ca, Ba, transition metal Fe, Zn, rare earth metals La, Eu and main group. Eight coordination polymers were synthesized by solvothermal and ambient temperature evaporation of metal Pb. Only 2,5-H2Br2BDC was found in eight of the coordination polymers. The results show that the three auxiliary carboxylic acid ligands may also play a role in conditioning pH. Four complexes [Zn (Br2BDC) were obtained by using lactic acid as auxiliary carboxylic acid ligand. (DMF)] (4, [Fe2 (Br2BDC) 2 (DMF) 3] (5), [Ba (Br2BDC) (DMF) (H20)] (6), [Pb (Br2BDC) (DMF)] (7). Complex 4 consists of a trapezoidal chain in a parallel ab plane with a uuuuuuuuuuu ABAB... Complex 5 is a three-dimensional framework consisting of one-dimensional square channels and 41 helical chains through shared metal nodes. Complex 6 is a three-dimensional metal-organic framework with a PCU topology. Complex 7 is a brick-wall two-dimensional network through a Br2BDC ligand. Three ligands [Ba2 (HBr2BDC) 2 (Br2BDC) (DMF) 2 (H2O) 2] (8), [La2 (Br2BDC) 3 (DMF) 4 (H2O) 2] (9) and [Eu2 (Br2BDC) 3 (DMF) 2 (H2O) 2 (10)] were obtained by using bromoacetic acid as an auxiliary ligand. Similarly, all of the metal-organic frameworks with one-dimensional channels along the b-axis are composed of Binuclear metals. Only the complex [Ca2 (Br2BDC) 2 (DMF) 2 (H2O) 2] (11) was obtained by using a rigid 3,5-pyridinedicarboxylic acid as an auxiliary ligand. The structure of complex 11 is a double self-penetrating nbo-like three-dimensional framework. The diverse bridging patterns of BDC ligands contribute to the construction of diverse structural complexes.
【学位授予单位】：山东科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4
【相似文献】
相关博士学位论文 前10条
1 梁玲玲;基于柔性含氮多羧酸配体的轴酰配位聚合物的合成、结构与性质研究[D];西北大学;2017年
2 刘志强;基于4-咪唑基配体金属有机框架化合物的构筑及其识别和吸附性能研究[D];南京大学;2017年
3 薛云珊;基于四面体型羧酸配体构筑新型功能配位聚合物及性质研究[D];南京大学;2014年
4 姜维;基于卟啉配体构筑的金属—有机框架的合成及催化性质研究[D];东北师范大学;2017年
5 赵念;分子/超分子结构基元构筑的新型金属有机框架的结构及性质研究[D];吉林大学;2017年
6 董玉伟;可调发光吡啶亚胺金属配合物的合成与荧光性能研究[D];哈尔滨工业大学;2017年
7 张航;间苯二酚杯[4]芳烃羧酸配体构筑的配位聚合物的发光性质研究[D];东北师范大学;2017年
8 匡政坤;基于配体相似性谱的药物设计方法及应用[D];华中农业大学;2016年
9 赵彦武;镧系、过渡金属功能配合物的构筑及荧光性质、手性传感的研究[D];山西师范大学;2017年
10 张誉腾;新型钒多酸基金属有机多面体的结构、自组装合成和性能研究[D];东北师范大学;2017年
相关硕士学位论文 前10条
1 万毅;含刚性羧酸配体配合物的结构和性质[D];山东科技大学;2017年
2 程佳佳;吡啶多羧酸配体构筑的配聚物的合成、结构及性能研究[D];郑州大学;2017年
3 高宽;多齿四氮唑配体构筑配合物的催化性能及中心金属离子交换的研究[D];郑州大学;2017年
4 徐亚州;2,2’-联吡啶衍生物为配体的磷光铼配合物的合成与性质分析[D];长春理工大学;2017年
5 夏勇;氮杂环鳌合配体亚铜配合物的合成、表征和光物理性质研究[D];江西理工大学;2017年
6 高瑞程;刚性硝基—联苯羧酸和吡啶羧酸配体功能性配位聚合物的构筑及磁性、荧光性能研究[D];西北大学;2017年
7 晏妮;唑类配体的刚性和柔性对配位聚合物结构和性质的影响[D];西北大学;2017年
8 孙文燕;手性联萘配体衍生的镁配合物的合成、结构及其在不对称氢膦化反应中的应用研究[D];西南大学;2017年
9 崔艳慧;吡啶羧酸类配体构筑的新型功能配合物的合成、晶体结构及性质研究[D];兰州大学;2017年
10 朱满;基于多羧酸配体构筑的多孔配位聚合物的合成与质子传导和荧光特性研究[D];东北师范大学;2017年
，本文编号：2209744
本文链接：https://www.wllwen.com/kejilunwen/huaxue/2209744.html
教材专著
