基于1，3-金刚烷二甲酸配位聚合物的构筑及其性能研究

【作者】 金俊成；

【导师】 王尧宇；

【作者基本信息】 西北大学 ， 无机化学， 2010， 硕士

【摘要】 设计和合成具有新颖结构和性质的配位聚合物已经展现了许多激动人心的新前景。最近,人们对设计和合成具有特定结构的金属有机框架的研究尤为火热。这不仅仅是因为它们有迷人的结构,更为重要的是它们在气体吸附,分子筛,离子交换和催化等方面有重要的潜在应用价值。然而,带有独特结构和功能的金属有机框架的自组装被许多因素所影响,如金属与有机配体的摩尔比,有机配体的本性,金属离子,体系中的溶剂分子,反应的温度,补偿离子和pH值等。因此,在现阶段去合成预知产物仍然是一项很大的挑战。本论文是在晶体工程组装原理的指导下,以1,3-金刚烷二甲酸配体为结构基块,通过选择特定的辅助配体和金属离子,合成得到了十六例配合物：{[Ag6(ADC)3(H2O)1.5]2·5.18H20}n (1),{[Ag(bpa)(HADC)]}n (2), {[Ag(bpp)(HADC)]·CH3OH}n (3),{[Ag4(bpe)3(ADC)2]·2H2O}n (4), {[Ag(bipy)(HADC)]·H2O}n (5),{[Ag2(bipy)2(ADC)]·6H2O}n (6), [Ag8(bpdap)4(ADC)4]·2C2H5OH·6H2O (7), [Zn(phen)(ADC)(H2O)]2·CH3OH (8), {[Zn(ADC)(bpe)]·H2O}n (9),{[Zn(ADC)(bipy)]·2H2O}.(10),{[Zn(ADC)(bpa)]2·5H2O}n(11), {[Zn(ADC)(bpp)]2·CH3OH}n (12),{[Zn(ADC)(bpp)]}n (13) {[Co(ADC)(bpp)(CH3OH)(H2O)].CH3OH·2H2O}n (14),{[Co(ADC)(bpp)]}n (15)和{[Cd2(ADC)2(bpp)3(H2O)]2·8H2O}n(16).X-对线单晶衍射分析结果表明：配合物1与配合物4分别是六核和四核的银簇；配合物2和配合物3为双核结构；配合物5和6为一维的无限链结构；而配合物7为不连续的八核银单元；配合物8为双核的寡聚物；配合物9是二维的层结构；配合物10和11结构类似,为一维链结构；配合物12是二维的带着(4,4)拓扑的二重穿插网络：配合物13,14和15均有手性空间群P212121,配合物13和15在本质上是同构的,都具有三重穿插的三维金刚烷网络结构；而配合物14为二维的格子结构；配合物16是维的带有内消旋结构的金属有机纳米管道。此外,运用元素分析、红外光谱、荧光光谱、热分析、X-射线粉末衍射等技术对配合物的性质进行了表征。更多还原

【Abstract】 Design and synthesis of the coordination polymers exhibiting novel structures and properties have provided exciting new prospects. Recently, considerable progress has been made in the design and synthesis of specific metal-organic frameworks (MOFs) which are highly active areas of investigation because of their intriguing structures and, more importantly, their potential applications in gas storage, molecular sieves, ion exchange, and catalysis. However, the self-assembly of MOFs with unique structure and function is influenced by many factors, such as the metal-to-ligand molar ratio, the nature of organic ligands, metal ions, solvent molecules, reaction temperature, counterion, and pH value of the solution. Therefore, it is a great challenge to synthesize the predicted products at this stage. In this paper, we select 1,3-adamantanedicarboxylic acid as building blocks to construct coordination polymers with selected transition metal ions and auxiliary ligands guided by assembly principle of coordination polymer crystal engineering. We have synthesized 16 coordination polymers. They are listed as follows:complexes 1 and 4 are formed by hexanuclear and tetranuclear Ag(I) clusters with weak Ag-Ag interactions; complexes 2 and 3 are dinuclear structures; 5 and 6 exhibit an infinite 1D chain structure,; whereas 7 is a discrete octanuclear Ag(Ⅰ) unit; complex 8 forms a OD dinuclear with closed loop unit; the complex 9 is a 2D layer framework.; compounds 10 and 11 are isomorphous with a small discrepancy and present one-dimensional chain-like structures; compound 12 is a 2D interpenetrated network with (4,4) topology; compounds 13,14 and 15 crystallize in a chiral space group P212121. The high dimensional 13 and 15are essentially isostructural, and present a 3-fold interpenetrated 3D diamondoid network; whereas 14 exhibits a 2D grid layer with left-handed helical chain; compound 16 is a meso-helical one-dimensional structure showing independent metal-organic nanotube (MONT). Furthermore, the elemental analysis, IR spectra, thermal stability, X-ray powder diffraction and the luminescent properties for the compounds are also discussed.更多还原