氮杂环羧酸配体配位聚合物的构筑、结构与性质表征

发布时间：2018-05-17 20:22

本文选题：配位聚合物 + 金属-有机骨架　；参考：《西北大学》2015年博士论文

【摘要】：配位聚合物(CPs)及金属-有机骨架化合物(MOFs)是指以金属离子或其簇作为节点,有机多齿桥联配体为连杆自组装形成的具有周期性网络结构的低密度晶态材料。因其层出不穷的结构和潜在的应用价值而备受关注。特别是MOFs作为新一代超低密度和孔结构高度有序多孔材料,由于其通常具有结构多样、溶解度低、孔径大小与形状及表面性质可调等特点,在过去二十年间得到迅猛发展,成为材料和化学领域的研究热点之一。有序的结构特征也使得其尤为适合用来研究结构-性能关系。尽管目前各种各样的CPs和MOFs被人们不断地合成出来,但设计合成有特定结构和性能的CPs和MOFs化合物仍然是非常具有挑战性的工作。这是因为它们的结构和性能不仅与其构筑基元即有机配体和金属离子有关,而且还往往受到各种合成条件的影响。因此除了精心设计有机配体外,研究这些条件对化合物结构的影响是非常必要的。目前,相对于苯环芳香多羧酸配体而言,功能化的氮杂环羧酸配体目前研究相对较少,基于以上考虑,本论文在配位化学、超分子化学及晶体工程的原理下,选用不同基团功能化、大小和形状也不同的有机配体来构筑CPs/MOFs,主要研究配体大小,刚柔性,功能化基团及配体的齿数和角度等对配合物结构和性质的影响。第一章,通过调节反应条件,利用甲基功能化的V型半刚性配体4-(2-甲基-1-咪唑基亚甲基)苯甲酸(HL1)在水热条件下与不同过渡金属盐反应合成了5例CPs,它们分别是：[Zn(L1)2]n(1)、{[Zn(L1)2]·(H2O)}n(2)、{[Cd(L1)2]-(H2O)}n(3)、{[Co(L1)2]·(H2O)2}n (4)、[Cu(L1)2]n(5)。单晶结构测试表明1和2中都含有单手性的2D螺旋层,不同的是1中两个同手性的螺旋层相互贯穿形成2D→2D的平行穿插结构,整个单晶结构是单手性的,但固体样品的圆二色谱测试表明其是外消旋混合物。而2的结构中则含有两种不同手性的2D螺旋层,它们堆积形成内消旋产物。2和3是同构的,4和5则是不同形式的1D串珠链结构。主要研究了化合物1对过渡金属离子和溶剂分子的荧光识别性能；实验结果表明其可以在水相中高选择性识别Cu2+离子；对于有机溶剂则可以专一的识别硝基苯类分子。第二章,我们选用目前较少被研究的2-氟异烟酸(HL2)和5-氟烟酸(HL3)在不同条件下与多种金属盐和氮杂环辅助配体合成了8个具有不同结构特征的过渡金属配合物。它们的结构简式分别为：[Cd(L2)2(bpe)]n (6)、[Ag(L2)]n (7)、{[Cu(L3)2(H2O)]-H2O}n (8)、[Cu(L3)2]n (9)、[Cu2(L3)4(bpy)(H2O)2]n (10)、[Co(L3)2 (H2O)4]n(11)、[Co(L3)2(bpe)]n(12)和[Co(L3)2(bpp)2(H2O)]n (13)。其中6和12是相似的一维梯子链结构,7是1D直线链结构,8和9是3D骨架结构,10是2D波浪型网格结构,11是一个单核化合物,而13则是1D折线型单链结构。分别表征了它们的粉末X-射线衍射(XRD)、红外光谱、热重等性质；对6和7进行了室温固态荧光光谱研究；对9和12则测试了其变温磁学性质。在第三章中,利用刚性含毗啶基团(路易斯碱性)作为活性基团的角形四羧酸配体2,6-吡啶-5,5'-二(间苯二甲酸)(H4L4)作为连接体构筑单元,在水热条件下利用其与过渡金属离子(Zn2+、Mn2+)成功合成两例具有(3,4,6)连接的拓扑类型为twf-d的笼状纳米孔洞结构的MOFs化合物,即：{[Zn2(L4) (H2O)1.5]·(xGUEST)}n(14)和 {[H2N(CH3)2]0.25[Mn3.75 (L4)1.5(Cl)0.75(HCOO)(DMF) (H20)0.675]·(xGUEST)}n(15)。结构分析表明它们的结构中均含有两种或多种无机SBU(包括罕见的联轮桨SBU)和孔径大小不同的空穴,即通过控制多个羧基配位基团在配体中的分布成功实现了多个次级构筑单元组装的异质性即复杂多样性MOFs。化合物14的荧光测试表明其在固态和溶剂中表现出不同机理的发光行为；气体吸附实验表明它们均对CO2气体具有选择性。
[Abstract]:Coordination polymers (CPs) and metal organic framework compounds (MOFs) are low density crystalline materials with periodic network structures formed by metal ions or their clusters as nodes and organic multi tooth bridging ligands self assembled for connecting rods. Because of their endless structure and potential value, MOFs is a new generation. Highly ordered porous materials with ultra-low density and pore structure have been developed rapidly in the past twenty years because of their characteristics of diverse structure, low solubility, pore size, shape and surface properties, which have become one of the hot topics in the field of materials and chemistry. Structure and performance relationships. Although a variety of CPs and MOFs are constantly being synthesized, it is still a very challenging task to design and synthesize CPs and MOFs compounds with specific structures and properties. This is because their structure and properties are not only related to the structural elements that are organic ligands and metal ions, but also often Therefore, it is necessary to study the effects of these conditions on the structure of the compounds in addition to the careful design of organic compounds in vitro. At present, the functionalized nitrogen heterocyclic carboxylic ligands are relatively less studied than the phenyl aromatic polycarboxylic ligands. Based on the above consideration, this paper is in coordination chemistry and supramolecular. Under the principle of chemical and crystal engineering, CPs/MOFs is constructed by using different functional groups, size and shape of organic ligands. The effects of ligand size, stiffness, function group and tooth number and angle on the structure and properties of the complex are mainly studied. Chapter 1, by adjusting the reaction conditions, using the methylation V type The semirigid ligand 4- (2- methyl -1- imidazolyl) benzoic acid (HL1) synthesized 5 cases of CPs with different transition metal salts under hydrothermal conditions. They are [Zn (L1) 2]n (1), {[Zn (L1) 2] (2), 4, 5. Single crystal structure tests show that 1 and 2 contain mono chiral The spiral layer, which is different in that 1 of the two helix layers of the 1 chiral helix penetrate into the parallel interpenetrating structure of the 2D, and the whole single crystal structure is mono chiral, but the round two chromatographic test of the solid sample indicates that it is a raceme mixture. The structure of the 2 contains two different chiral 2D helix layers, which accumulate to form internal raceme products.2 and 3. It is isomorphic, 4 and 5 are different forms of 1D string structure. The fluorescence recognition performance of compound 1 for transition metal ions and solvent molecules is mainly studied. The experimental results show that it can identify Cu2+ ions high selectively in the water phase; for organic solvents, we can identify nitrobenzene molecules in a special way. Chapter second, we choose the order. The less studied 2- fluoro nicotinic acid (HL2) and 5- fluoric acid (HL3) synthesized 8 transition metal complexes with various metal salts and nitrogen heterocyclic auxiliary ligands under different conditions. Their structure simple forms are [Cd (L2) 2 (BPE)]n (6), [Ag (L2)]n (7), {[Cu (9), 4 (9) 4). Bpy) (H2O) 2]n (10), [Co (L3) 2 (H2O) 4]n (11), [Co (L3) 2 (BPE)]n (12) and [Co (13) 2 (13). Of which 6 and 12 are similar one-dimensional ladder chain structures, 7 are linear chain structures, 8 and 9 are skeleton structures, 10 are wavy grid structures, and are a single core compound. Final X- ray diffraction (XRD), infrared spectrum, thermogravimetry, and other properties; 6 and 7 were studied at room temperature by solid-state fluorescence; the temperature magnetic properties were tested for 9 and 12. In the third chapter, the angular four carboxylic acid ligand, 2,6- pyridine -5,5'- two (H4L4) (H4L4), as the active group, was used as the active group. In the hydrothermal condition, two cases of MOFs compounds with caged nanopore structure of (3,4,6) connection twf-d are successfully synthesized under hydrothermal conditions, namely, {[Zn2 (H2O) 1.5] (xGUEST)}n (14) and 1.5 (H2O) 0.75. ST)}n (15). Structural analysis shows that their structures contain two or more inorganic SBU (including rare wheel propeller SBU) and holes with different aperture sizes, that is, by controlling the distribution of multiple carboxylic ligands in the ligand, the heterogeneity of multiple secondary architecture units is successfully realized, namely, the fluorescence of complex diversity MOFs. compound 14 The results show that they exhibit different mechanisms of luminescence in solid state and solvent. Gas adsorption experiments show that they all have selectivity for CO2 gas.
【学位授予单位】：西北大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：O641.4

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