穿插和缠绕金属—有机骨架化合物的构筑和性能研究
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摘要
配位功能材料的研究重点已从合成、结构表征转变为性能方面的研究,主要体现在研究结构和性能的构效关系以及开发性能更优异的复合杂化材料。运用分子设计和晶体工程中的有关原理和方法,对金属-有机骨架化合物材料实现功能上的分子剪裁和分子组装,使之具有新颖结构和优良性能,是现代配位功能材料研究的发展趋势之一,已经引起广大科学工作者的极大关注。穿插和缠绕现象是宏观世界中普遍存在的现象,然而在微观世界中,穿插和缠绕由于其自身结构的特殊性而并非常见。金属-有机骨架化合物往往会发生穿插和缠绕现象,常见的穿插和缠绕类型有:0D→1D;1D→1D;1D→2D;1D→3D;2D→2D;2D→3D;0D+0D→1D,1D+2D→3D等。结构上的新颖性使金属-有机骨架化合物功能材料具备了更独特的性质,成为了配位化学领域的一大研究热点。
     本论文致力于利用不同柔性羧酸类配体与过渡金属构筑具有新颖拓扑的缠绕网络金属-有机骨架化合物,研究和分析这些金属-有机骨架化合物的合成条件及规律、考察网络的拓扑类型、分析网络所属的缠结类型,并探索它们结构和性能间的构效关系。全文共分5章。
     1、第一章阐述了金属-有机骨架化合物定义、发展历程、及分类和潜在的应用价值。重点介绍了此类化合物的合成手段和各类型互穿网络化合物的结构和性能特征,以及对新颖穿插和缠绕结构化合物的研究进展进行了归纳和总结,最后对论文选题意义和进展做了概述。
     2、第二章介绍了通过选用一个柔性芳香二羧酸作为主配体,中性的吡啶衍生物作为辅助配体和金属自组装,构筑了9个聚合物。它们具有不同的维数、拓扑类型和性能,其中同构的聚合物1-3为目前报道的第一例四回路锁烃。同时分析了金属离子类型对构筑互穿聚合物结构和性能的影响。
     3、第三章介绍了通过不同的柔性羟基多元羧酸与吡啶类组成混合配体的方法,合成了一系列分别为零维、一维、二维和三维结构的配合物,分析了羟基多元羧酸的配位模式、辅助配体的尺寸大小和反应合成条件对构筑配合物的互穿类型和性能的影响。此外,聚合物14包含了三种金属,对其进行初步磁性分析表明了强的反铁磁性,其磁性理论计算正在进行中,聚合物13则表现了强的铁磁性。
     4、第四章阐述了选用咪唑[4,5-f][1,10]邻二氮杂菲和不同构型的羧酸类配体联用来自组装,得到了系列化合物。对咪唑[4,5-f][1,10]邻二氮杂菲配体的配位化学进行了研究,引入柔性多元芳香羧酸易于构筑缠绕结构的化合物,此外,金属离子的不同类型对构筑化合物维数有明显的影响。此类化合物表现了有趣的发光行为。5、第五章介绍了通过溶剂热方法得到二种不同缠绕类型的金属-有机骨架化合物。第一类为目前报道的分子辫股数最高的六股分子辫;第二类为2D→3D三重穿插6-节点的22.48.65 (Schlafli symbol)网络,在该聚合物中,包含了一个罕见的双核轮浆Co2(CO2)4二聚体单元。
The research priority of coordination functional material is changing from synthesis, structure characterizations to functional properties, its characteristics are mainly embodied in two aspects:investigate the relationship of structure and property and explore advanced composite material with more superior properties. Employment of related principle molecular designing and crystal engineering was used to modify and assemble the metal-organic frameworks(MOFs) polymers materials and would be boost the novel topological frames and special functions of the sets, which has been greatly attracted in the materials field. In addition, entanglement and interpenetration is a popular phenomenon in the macrocosm, however, in the microcosm system; it is not universal due to the structural particularity of its own. Entangled and interpenetrated examples are always observed in MOFs compounds, which exhibit common types:including 0D→1D;1D→1D;1D→2D;1D→3D;2D→2D; 2D→3D; 0D+0D→1D,1D+2D→3D, and so on. As structure determines property, structural peculiarity of entangled and interpenetrated networks will reinforce the skeleton rigidity and porosity of the whole frame, thereby generating some peculiar functional properties, which became a new research hotspot in coordination chemistry.
     The aim of this thesis is to prepare new types of entangled MOFs compounds on the basis of flexible ligands and transition metal, to study the synthetic conditions and rules for these compounds, discuss the topological types, and to explore the relationships between structures and properties for the sets of compounds. This work includes five chapters.
     1. Chapter 1 gives an introduction of the definition, development history, classify and potential functions of MOF compounds, especially, discuss the synthesized methods, the characteristics of types of entanglement and interpenetrated MOFs compounds and their peculiar functional properties, as well as the program of novel entanglement and interpenetrated MOFs compounds. The aim and progress of this work have been outlined.
     2. In chapter 2, by mixing a typical example of a long, V-shaped, flexible ligand 4,4'-oxybis(benzoic acid) (H2oba) and N-containing ligands in the presence of transition metal ions, nine coordination polymers have been synthesized, which have kinds of dimensions, topological types and functional properties. Three isologues of compounds 1-3 have unprecedented topologies, which present the first example of 4-crossing catenane motifs. The effect of metal ions on the structures and properties of MOFs was also discussed.
     3. In chapter 3, by mixing flexible hydroxycarboxylic acid and assistant ligands in the presence of transition metal ions, a series of compounds have been prepared, which exhibit zero-dimensional to three-dimensional structural frames. It has been demonstrated that the coordinated modes of ligands of hydroxycarboxylic acid, the size of assistant ligand and the synthesis conditions are critical to the resulting architectures. Besides, the heterometallic compound 14 has a strong antimagnetic behavior, which has been theoretically calculated and simulated for its magnetism, while polymer 13 features a strong ferromagnetism.
     4. Chapter 4 reports the coordination chemistry of 1H-imidazo[4,5-f][1,10]-phenanthroline in the absence/presence of the different conformations of carboxylate under mild conditions, series of compounds have been obtained. The result indicates that new interpenetrating and entangled MOFs higher-nuclear compound can be obtained successfully by introducing flexible multi-carboxylate ligands, the metal radium affects the dimensions obviously. Some of compounds exhibit strong luminescence characters.
     5. In chapter 5, two types of interpenetrating and entangled MOFs polymers are synthesized by solvthermal reactions. The first one is composed of sextuple-stranded molecular braid, which represents the highest stranded number of molecular braid; the second set features threefold 2D→3D parallel interpenetrated net with a Schlafli symbol of 22.48.65 and contains one interesting Co2(CO2)4 paddle-wheel unit.
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