稀土和过渡金属有机骨架化合物的合成、结构及性质研究

发布时间：2018-05-12 14:03

本文选题：金属有机骨架 + 水热/溶剂热合成　；参考：《吉林大学》2017年硕士论文

【摘要】：金属有机骨架化合物拥有多变的骨架结构,在多个领域如气体分离和储存、催化、药物释放、传感、发光和分子磁性等领域具有潜在的应用价值,因而引起人们广泛的研究热情。如今人们致力于开发多孔发光材料,期望可以用于检测空气中的小分子污染物和去除水体系中的有机染料。在金属有机骨架化合物的研究过程中,合理地选择金属中心和有机配体可有目的的组装具有特定化学和物理性质的MOFs。芳香族羧酸配体拥有多样的配位模式以及如氢键相互作用和π…π堆积等超分子相互作用,是一类在MOFs骨架的合成中使用广泛的多功能有机配体。多羧酸有机配体由于更多样的配位模式和更复杂的超分子相互作用,在MOFs研究中备受重视。例如:2,6-萘二羧酸具有多种配位模式,高对称性和结构刚性,作为优良的桥连配体可以用来构筑出具有独特拓扑结构和优异性质的MOFs。近来,具有多羧基的联苯四羧酸越来越引起人们的关注,2,2’,4,4’-联苯四羧酸与关注度较高的3,3’,5,5’-联苯四羧酸相比,在MOFs领域还没有被充分的探索。由于2-和2’-羧酸官能团之间的位阻作用,两个苯环平面存在一定角度,所以2,2’,4,4’-联苯四羧酸可以被看作是一个扭曲的Π-状有机次级结构单元(SBU)。这样一个独特的SBU与几何构型多样的无机SBUs结合,可能会组装出具有独特拓扑结构的MOFs。2,3’,4,5’-联苯四羧酸具有较低的对称性,展现了独特的配位几何结构,而且基于2,3’,4,5’-联苯四羧酸的MOFs很少被报道。此外,引入第二配体是一个构筑新颖结构MOFs的重要方法。例如,在以芳香羧酸为有机配体的合成中,引入棒状有机配体4,4’-联吡啶常常有利于诱导高维数骨架的生成。本论文的主要研究成果如下:1、在溶剂热条件下,以刚性芳香二羧酸2,6-萘二羧酸(2,6-H_2NDC)为有机配体,以稀土元素为中心合成了八个新型同构的RE-MOFs,{[RE_2(NDC)_3(H_2O)_4]·(DMF)_4}n(RE=Eu(1),Gd(2),Tb(3),Er(4),Yb(5),Dy(6),Y(7),Lu(8))。对其拓扑结构分析表明,产物为一个2,4,5-连接的三维网络,其Sch?fli符号为(42.62.82)2(42.63.85)2(6)。对化合物1-8性质研究表明:八个化合物均表现出良好的热稳定性和溶剂稳定性;化合物1,2,5,7,8表现出良好的发光性能。同时,化合物1对小分子有机溶剂表现出良好的传感性能;化合物2的活化产物2A对有机染料表现出良好的吸附性能,尤其是对结晶紫染料(CV+)的吸附性能最好。因此,化合物1可以用来检测小分子有机污染物,化合物2的活化产物2A可以用来移除水溶液中的有机染料。这些结果表明,RE-MOFs在发光材料特别是化学传感和发光温度计方面具有潜在的应用价值。(第二章)2、在溶剂热条件下,以刚性配体2,6-萘二羧酸(2,6-H_2NDC)为有机配体,同时引入4,4’-联吡啶为第二配体,以过渡金属锌为中心合成了一个1D链状MOF,[Zn_2(4,4’-Bipy)(CH3COO)_4H_2O](化合物9)。在水热条件下,以2,2’,4,4’-联苯四羧酸和2,3’,4,5’-联苯四羧酸为有机配体,以过渡金属锌为中心分别合成了一个2D层状MOF,H_4[Zn_5(BPTC)_2O_2(OH)_2(H_2O)_4](化合物10)和一个3D网状MOF,[Zn(H_2BPTC)]n(化合物11)。化合物9-11均表现出良好的发光性能。这项工作表明,化合物9-11在发光方面具有潜在的应用价值。(第三章)
[Abstract]:Metal organic skeleton compounds have a variety of framework structures, which have potential applications in many fields, such as gas separation and storage, catalysis, drug release, sensing, luminescence and molecular magnetism. Therefore, people have a wide range of research enthusiasm. Nowadays, people are working to develop porous luminescent materials and expect to be used in the detection of air. In the study of organometallic skeleton compounds, the rational selection of metal center and organic ligands in the study of metal organic framework compounds can be used to assemble the MOFs. aromatic carboxylic ligands with specific chemical and physical properties to have a variety of coordination modes, as well as hydrogen bond interaction and pi... The supramolecular interaction, such as pion accumulation, is a class of multifunctional organic ligands used in the synthesis of MOFs skeletons. Polycarboxylic ligands have attracted much attention in MOFs research because of more complex coordination modes and more complex supramolecular interactions. For example, 2,6- naphthalene two carboxylic carboxylic acids have a variety of coordination modes, high symmetry and structural rigidity. As a good bridging ligand, it can be used to construct MOFs. with unique topological structure and excellent properties. The polycarboxylic benzyl four carboxylic acid has attracted more and more attention. 2,2 ', 4,4' - biphenyl four carboxylic acid has not been fully explored in the field of MOFs compared with the higher 3,3 ', 5,5' - biphenyl four carboxylic acid. 2- and 2 '- carboxylic functional groups have a hindrance, two benzene rings have a certain angle, so 2,2', 4,4 '- biphenyl four carboxylic acid can be regarded as a twisted organic secondary structure unit (SBU). Such a unique SBU is combined with a variety of inorganic SBUs with geometric configuration and may assemble a M with a unique topological structure. OFs.2,3 ', 4,5' - biphenyl four carboxylic acids have relatively low symmetry, exhibit unique coordination geometric structures, and MOFs based on 2,3 ', 4,5' - biphenyl four carboxylic acids are rarely reported. In addition, the introduction of second ligands is an important way to construct a novel structure MOFs. For example, in the synthesis of aromatic carboxylic acids as organic ligands, a rod is introduced. The main research results in this paper are as follows: 1, eight new isomorphic RE-MOFs, {[RE_2 (NDC) _3 (H_2O) _4] (DMF) _4}n (DMF) _4}n (DMF) _4}n (RE=), were synthesized under the solvothermal condition, with the rigid aromatic two carboxylic acid naphthalene two carboxylic acid (2,6-H_2NDC) as the organic ligand. Eu (1), Gd (2), Tb (3), Er (4), Yb (5), Dy (6), Y (7), Lu (8)). The analysis of its topology shows that the product is a three dimensional network of 2,4,5- connection, and its Sch? Fli symbol is (42.62.82) 2 (6) 2 (6). The study of compound 1-8 shows that all compounds exhibit good thermal stability and solvent stability; compound exhibits good performance. Good luminescence properties. At the same time, compound 1 shows good sensing performance for small molecular organic solvents, and compound 2's activation product 2A shows good adsorption properties for organic dyes, especially for crystal violet dye (CV+). Therefore, compound 1 can be used to detect small molecular organic pollutants and the activation of compound 2. The product 2A can be used to remove organic dyes in aqueous solutions. These results show that RE-MOFs has potential applications in the luminescent materials, especially chemical sensing and luminescence thermometers. (second) 2, under the solvothermal condition, the rigid ligand 2,6- naphthalene two carboxylic acid (2,6-H_2NDC) is the organic ligand, and 4,4 '- bipyridine is introduced to second Ligands, a 1D chain like MOF, [Zn_2 (4,4 '-Bipy) (CH3COO) _4H_2O] (compound 9) is synthesized at the center of transition metal zinc. Under the hydrothermal condition, 2,2', 4,4 '- biphenyl four carboxylic acid and 2,3', 4,5 '- biphenyl four carboxylic acid are used as organic ligands. (compound 10) and a 3D network MOF, [Zn (H_2BPTC)]n (compound 11). Compound 9-11 showed good luminescence performance. This work shows that compound 9-11 has potential application value in luminescence. (third)

【学位授予单位】：吉林大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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