基于氮杂环衍生桥连配体形成的新型配位聚合物的合成、结构及表征

发布时间：2018-08-27 16:22

【摘要】：在过去的十年中,金属-有机配位聚合物(或金属-有机框架,MOFs)的设计合成、结构和性质的研究在超分子化学和晶体工程领域已经被目睹有显著的提高。不仅由于它们在催化、分离、离子交换等领域中有广泛的潜在应用,也因为它们的充满美学的拓扑和有趣的结构。随着晶体学及相关学科的发展,通过选择有机配体和金属离子合成具有特定结构的金属-有机配位聚合物,受到人们广泛的关注。本论文致力于利用氮杂环衍生桥连配体与过渡金属离子,通过水热反应法制备具有良好的荧光或磁性的新型金属-有机配位聚合物,从而进一步研究新型金属-有机配位聚合物的合成、结构和性能之间的关系。利用水热合成法,合成了一系列新型的金属-有机配位聚合物,通过元素分析、ICP、IR光谱、单晶X-射线衍射分析和X-射线粉末衍射分析(XRPD)对晶体结构进行了表征,并对配位聚合物的热稳定性(TG)、荧光性质和磁学特性进行了表征与初步的研究。1.利用氮杂环类桥连配体,在水热条件下成功合成了五例新型的金属-有机配位聚合物:[Zn_2(bdc)_(1.5)(dbpp)](1)[Cd(dbpp)_2(H_2O)·(H_2O)](2)[Co(dbpp)_2](3)[Cu(tyty)](4)[Cu_(1.5)(L1)(L2)(tyty)](5)(dbpp=4-{1-[4-(2,5-Dihydro-1H-tetrazol-5-yl)-benzyl]-1H-pyrazol-3-yl}-pyridine,bdc=1,4-benzenedicarboxylate acid,HL1=2,3,4,5-tetrachlorobenzoic acid,HL2=2,3,4,5,6-pentachlorobenzoic acid,Htyty=1-(tetrazp-5-yl)-4(trizo-1-yl)benzene),配位聚合物1是一个迷人的三维自穿结构。配位聚合物2具有独特的(2D→3D)多连锁图案,并且每个单套网络均包含双边结构。配位聚合物3呈现迷人的缠结结构,同时具有多插指和伪多轮烷的特征。配位聚合物4呈现一个二维双-双层片状网络,此外每个片状层以平行模式与相邻层进行多插指,产生一个2D→3D的多插指框架。配位聚合物5呈现一个由tyty阴离子与棒状SBU构筑的二维层,并且二维层进一步呈现一个2D→3D多插指网络。2.在水热条件下,利用氮杂环羧酸配体成功构筑了三例新型的金属-有机配位聚合物:[Co(ppmba)_2](6)[Zn(ppmba)_2(H_2O)_(0.5)](7)[Cd(ppmba)_2·(H_2O)_(0.25)](8)(Hppmba=4-((3-(pyridin-4-yl)-1H-pyrazol-1-yl)methyl)benzoic acid),其中,配位聚合物6是一例特别的(2D→3D)多插指结构,并且每个单套网络均由双层组成。配位聚合物7和8是同构的,均呈现迷人的(2D→3D)缠结框架,并且同时具有多连锁和多插指的特征。论文主要内容如下:第一部分,对配位聚合物的形成与发展过程,合成方法以及配位聚合物的性能,应用以及分类等方面进行了论述。介绍了选题的目的和意义以及取得的主要结果。并且介绍了实验过程中所需要的化学试剂,实验仪器以及主要测试手段。第二部分,氮杂环类桥连配体与过渡金属离子成功合成了五例新的金属-有机配位聚合物。新的配位聚合物的合成方法,晶体结构,表征与性质。第三部分,氮杂环羧酸配体与过渡金属离子成功合成了三例新的金属-有机配位聚合物。新的配位聚合物的合成方法,晶体结构,表征与性质。
[Abstract]:In the past decade, the design, synthesis, structure and properties of metal-organic coordination polymers (or metal-organic frameworks, MOFs) have been significantly improved in supramolecular chemistry and crystal engineering, not only because of their potential applications in catalysis, separation, ion exchange and other fields, but also because of their charge. The topology and interesting structure of Manchu aesthetics. With the development of crystallography and related disciplines, the synthesis of metal-organic coordination polymers with specific structures by choosing organic ligands and metal ions has attracted widespread attention. This paper is devoted to the hydrothermal synthesis of bridged ligands and transition metal ions derived from nitrogen heterocycles. A series of novel metal-organic coordination polymers have been synthesized by hydrothermal method. Elemental analysis, ICP, IR spectroscopy and single crystal X-ray diffraction were used to study the relationship between the synthesis, structure and properties of new metal-organic coordination polymers. The crystal structure was characterized by X-ray powder diffraction (XRPD). The thermal stability (TG), fluorescence and magnetic properties of the coordination polymers were characterized and preliminarily studied. 1. Five novel metal-organic coordination polymers [Zn_2 (bdc) (1.5) were successfully synthesized under hydrothermal conditions using nitrogen heterocyclic bridging ligands. )(dbpp)](1)[Cd(dbpp)_2(H_2O)路(H_2O)](2)[Co(dbpp)_2](3)[Cu(tyty)](4)[Cu_(1.5)(L1)(L2)(tyty)](5)(dbpp=4-{1-[4-(2,5-Dihydro-1H-tetrazol-5-yl)-benzyl]-1H-pyrazol-3-yl}-pyridine,bdc=1,4-benzenedicarboxylate acid,HL1=2,3,4,5-tetrachlorobenzoic acid,HL2=2,3,4,5,6-pentachlorobenzoic acid,Htyty=1-(tetrazp- 5-yl) -4 (trizo-1-yl) benzene, coordination polymer 1 is a fascinating three-dimensional self-piercing structure. Coordination polymer 2 has a unique (2D 3D) multi-chain pattern, and each single network contains a bilateral structure. Coordination polymer 3 has a fascinating entanglement structure, with the characteristics of multi-interpolation finger and pseudo-polycyclic alkane. In addition, each lamellar layer interacts with adjacent layers in parallel mode to produce a 2D 3D multi-interpolation frame. The coordination polymer 5 presents a two-dimensional layer constructed by tyty anion and rod SBU, and the two-dimensional layer further presents a two-dimensional three-dimensional multi-interpolation network. 2. Under hydrothermal conditions, nitrogen is utilized. Heterocyclic carboxylicacid ligands have successfully constructed three novel metal-organic coordination polymers: (Co (ppmba) _2] (6) [Zn (ppmba) _2 (Zn (ppmba) _2 (H_2O) (0.5)] (7) [Cd (ppmba) _2 ((ppmba) _2 ((H_2O) (0.25)] (8) (H ppmba = 4 - ((3 - (pyridin-4-yl) - 1H-pyrazozol-1-pyrazol-1-yl) methyl) methyl) acid, in which coordination polymer 6 is a special coordination polymer 6, coordination polymer 6 is a special 3D (3D) poly 858585858594 (3D) multi-dimensional (3D) multi-benzoic acid, Interpolation structure, and each single Complex polymers 7 and 8 are isomorphic, exhibit attractive (2D 3D) entanglement frameworks, and have the characteristics of multi-linkage and multi-interpolation. Five new metal-organic coordination polymers have been successfully synthesized by bridging ligands of heterocyclic nitrogen and transition metal ions. In the third part, three new metal-organic coordination polymers have been successfully synthesized by heterocyclic carboxylic acid ligands and transition metal ions.
【学位授予单位】：西南大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O634

【相似文献】