基于柔性羧酸配体构筑的功能性配位聚合物的合成、结构及光电性能研究

发布时间：2017-12-27 12:04

本文关键词：基于柔性羧酸配体构筑的功能性配位聚合物的合成、结构及光电性能研究　出处：《郑州大学》2016年硕士论文　论文类型：学位论文

【摘要】：金属有机框架(Metal-Organic Frameworks,MOFs)材料作为新型的多孔固态材料,凭借其多样化的结构特性和独特的构效关系吸引了研究者的广泛关注。构筑金属有机框架材料的配体可分为刚性配体和柔性配体。其中,柔性多羧酸配体本身存在可以自由旋转的柔性位点(C、O、N等原子),与金属离子构筑时,具有多变的配位模式,从而产生具有各种优异性能的配合物结构。金属有机框架材料在很多领域都有非常有前景的潜在应用价值。在气体分离、存储、光学材料、电学材料等方面的应用都在逐渐被探索中。另外,作为燃料电池的非常重要的组成部件,质子传导材料对燃料电池的性能起着至关重要的作用。金属有机框架材料的以其结构可预计性,在质子传导材料领域的应用研究得到了快速发展。同时,稀土金属离子配合物的独特发光性能,在荧光传感等领域也展现了诱人的应用前景,已经探索出了许多的应用实例。本论文中,我们主要开展了以下的工作:一、设计并合成了柔性芳香多羧酸配体H3L_1:5-(2-甲酰基-4-羧基苯氧甲基)间二苯甲酸(H3L_1=5-(4-Carboxy-2-formyl-phenoxymethyl)-isophthalic acid),并利用其与稀土金属铕离子,经由混合溶剂热方法,在不同混合溶剂和温度条件下分别得到了两种新型Eu-MOF:{[Eu(L_1)(H_2O)4]·H_2O}_n(1),{[Eu(L_1)(DMF)2]·(DMF)(H_2O)}_n(2),并对它们进行了X-射线单晶衍射、红外、元素分析、X-射线粉末衍射和热分析等测试,对所得配合物进行了表征。Eu-MOF1具有2D平面网格结构,通过配位水分子与配位羧基氧之间形成的氢键连接成3D超分子。Eu-MOF2是3D的框架结构,在垂直b轴方向存在大小约为9.0×10.0?2的一维孔道,孔道被配位DMF和游离DMF占据。两种Eu-MOF展现出了优异的红色发光性能,基于此我们尝试进行了硝基芳香性爆炸物的荧光检测和金属离子的荧光检测的研究。实验结果表明,在全部被检测的17种金属离子中,Fe3+使Eu-MOF的荧光几乎完全猝灭,而Fe2+的存在对Fe3+的检测有一定的影响。爆炸物硝基苯(NB)、2-硝基苯酚(2-NP)和三硝基苯酚(TNP)对配合物荧光产生猝灭,且在硝基苯(NB)、2-硝基苯酚(2-NP)和三硝基苯酚(TNP)蒸气氛中,配合物荧光强度随时间变化而降低。之后对硝基苯(NB)、2-硝基苯酚(2-NP)和三硝基苯酚(TNP)对配合物的荧光猝灭机理进行了研究。二、设计合成了配体H4L_2:5-(N,N-二羧甲基氨甲基)间苯二甲酸(5-[(Bis-carboxymethyl-amino)-methyl]-isophthalic acid),并利用其与过渡金属离子Co2+、Fe2+,在有辅助配体(L’)bpe(1,2-二(4-吡啶基)乙烯)或bpn(1,2-二(4-吡啶基)偶氮)存在的情况下,利用混合溶剂热法,在相同条件(反应溶剂,反应温度、时间等)下合成了{[M2(L_2)·(L’)·(H_2O)]·(H_2O)5.5}_n(M=Co(II),L’=bpe(3);M=Co(II),L’=bpn(4);M=Fe(II),L’=bpe(5)),并且通过X-射线单晶衍射、红外、元素分析、X-射线粉末衍射、热分析等测试技术,对所得配合物的结构进行了表征。并通过浸泡等方法,得到了封装有四氢呋喃、噻吩、吡咯等的晶体结构,并对一系列的结构做了交流阻抗等性质的测试,用以探究微观结构和质子载体种类对框架材料电导率的影响。
[Abstract]:Metal-Organic Frameworks (MOFs), as a new porous solid material, has attracted wide attention from researchers for its diverse structural characteristics and unique structure-activity relationship. The ligands of the metal organic frame materials can be divided into rigid ligands and flexible ligands. Among them, flexible polycarboxylate ligand itself has free rotation of flexible sites (C, O, N and other atoms). When it is built with metal ions, it has a varied coordination mode, resulting in the structure of complexes with various excellent properties. Metal organic frame materials have a very promising potential application value in many fields. The applications of gas separation, storage, optical materials, electrical materials and other aspects are gradually being explored. In addition, as a very important component of fuel cells, proton conducting materials play a vital role in the performance of fuel cells. The application of metal organic frame materials in the field of proton conduction materials has been developed rapidly because of its structural predictable properties. At the same time, the unique luminescent properties of rare earth metal ions complexes have shown attractive applications in fluorescence sensing and other fields, and many applications have been explored. In this thesis, we mainly carried out the following work: first, the design and synthesis of flexible aromatic polycarboxylate ligands H3L_1:5- (2- formyl -4- carboxyl methyl phenoxy benzoic acid (H3L_1=5-) two (4-Carboxy-2-formyl-phenoxymethyl) -isophthalic acid), and with the rare earth europium ion, via solvothermal method, respectively. Two new types of Eu-MOF:{[Eu in different solvent and temperature conditions (L_1) (H_2O) 4] and H_2O}_n (1), {[Eu (L_1) (DMF) 2] (DMF) (H_2O)}_n (2), and their X- ray single crystal diffraction, IR, elemental analysis, X- ray powder diffraction and thermal analysis test of the complexes were studied. Eu-MOF1 has a 2D plane grid structure, which is connected to a 3D supramolecular by the hydrogen bonds formed between the coordination water molecules and the coordination carboxyl oxygen. Eu-MOF2 is the framework of 3D, and there is a one dimension channel with a size of about 9 * 10? 2 in the direction of vertical b axis, and the channel is occupied by the coordination DMF and free DMF. The two kinds of Eu-MOF exhibit excellent red emitting properties. Based on this, we have tried the fluorescence detection of nitro aromatic explosives and the fluorescence detection of metal ions. The experimental results show that, in all the 17 metal ions detected, Fe3+ almost completely quenches the fluorescence of Eu-MOF, while the presence of Fe2+ has a certain effect on the detection of Fe3+. The explosives, nitrobenzene (NB), 2- nitrophenol (2-NP) and three nitrophenol (TNP) quenched the fluorescence of complexes, and the fluorescence intensity of complexes decreased with time in nitrobenzene (NB), 2- nitrophenol (2-NP) and three nitrophenol (TNP) vapor atmosphere. The fluorescence quenching mechanism of nitrobenzene (NB), 2- nitrophenol (2-NP) and three nitrophenol (TNP) was investigated. Two, design and synthesis of the ligand H4L_2:5- (N, N- two carboxymethyl An Jiaji) benzene two formic acid (5-[(Bis-carboxymethyl-amino) -methyl]-isophthalic acid), and the Co2+, Fe2+ and transition metal ions, aided by ligand (L 'BPE (1,2-) two (4- pyridyl) ethylene or BPN (1,2- two) (4- pyridyl) azo) exist, using mixed solvothermal method under the same conditions (solvent, reaction temperature and time) to synthesize {[M2 (L_2) - (L) - (H_2O)] - (H_2O) 5.5}_n (M=Co (II), L =bpe (3'); M=Co (II), L =bpn (4); M=Fe (II), L =bpe (5)), and by X- ray diffraction, IR, elemental analysis, X- ray powder diffraction, thermal analysis and testing technology, the structures of the complexes were characterized. The crystal structure of tetrahydrofuran, thiophene and pyrrole was obtained by immersion and other methods. A series of structures were tested for AC impedance and other properties, so as to explore the influence of microstructures and kinds of proton carriers on the conductivity of frame materials.
【学位授予单位】：郑州大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O641.4

【相似文献】