【作者】 陈勇强；

【导师】 卜显和；

【作者基本信息】 南开大学 ， 无机化学， 2013， 博士

【摘要】 本论文选用四种N/O多齿配体作为主配体,在溶剂／水热条件下合成了24个新的金属-有机框架化合物。通过单晶衍射、红外光谱、元素分析以及粉末衍射对它们的结构进行了表征。详细分析了它们的结构和拓扑,并对部分配合物的荧光性质、光催化活性、磁性以及气体吸附性质做了初步研究。主要内容如下：第一章,概述了配位聚合物的研究背景和多齿配体基配位聚合物的研究现状,在此基础上提出了本课题的选题依据。并且对本论文取得的主要进展做了概述。第二章,以三齿吡啶配体2,4,6-tris(4-pyridyl)pyridine (L1)为主配体,借助不同尺寸、柔韧性和形状的配体为辅助配体,与金属离子配位得到了10个金属-有机框架化合物,并对它们的结构进行了表征。配合物1代表了第一例具有二重互穿的lohl拓扑结构。此外,我们还研究了配合物1的光催化活性和磁性质。配合物1、5、6、9和10拓扑结构的不同,表明辅助配体的引入至关重要。第三章,引入多钼酸盐得到了配合物11和12两个杂金属基金属-有机框架材料。它们展现了相似的“层柱”结构,且包含杂金属纯无机层结构,光催化实验表明它们在紫外灯照射下能够降解甲基橙染料。配合物13具有四重螺旋孔道,水稳定性好,在水溶液中它能够通过简易的颜色变化来识别不同的无机阴离子。气体吸附测试表明,活化的配合物13在接近于室温下能够捕获CO2气体。第四章,合成了7个N/O多齿配体基金属-有机框架化合物。在相同的合成条件下,通过引入有机连接子实现了配合物16到17的结构转变。详细分析了合成条件对配合物结构的影响。磁性测试表明配合物16和17具有反铁磁行为。第五章,合成了4个包含金属簇单元的金属-有机框架化合物。配合物21的合成为这类结构的构筑提供了一种新的途径。并对配合物23和24的吸附和荧光性质进行了系统研究。第六章,全文总结。更多还原

【Abstract】 The aim of this thesis is the synthesis of new metal-organic frameworks (MOFs) based on four N/O multidentate ligands. Twenty-four new MOFs have been synthesized under the solvothermal or hydrothermal conditions and structurally characterized by single crystal X-ray diffraction, IR, elemental analyses and powder X-ray diffraction. The structures and topologies of these complexes have been analyzed in detail. And, the fluorescent, photocatalytic activity, magnetic and gas adsorption properties of part of complexes have also been investigated. The main contents of this work are summarized as below:In chapter1, a brief introduction of the research background of coordination polymers and the current progresses of coordination polymers based on multidentate ligands have been reviewed. Based on the aforementioned review, the foundation of this thesis has been introduced. Moreover, the progresses of this thesis have been outlined.In chapter2, we selected some auxiliary ligands with different size, flexibility and shape, and ten MOFs have been synthesized and structurally characterized based on2,4,6-tris(4-pyridyl)pyridine ligand. Complex1represents the first example of interpenetrated coordination framework with unique (3,6)-connected lohl topology. Furthermore, the photocatalytic activity and magnetic properties of1have been investigated. The structural difference of complexes1,5,6,9and10indicates that organic carboxylate ligands play important roles in the formation of such coordination architectures.In chapter3, two metal-organic hybrids (complexes11and12) have been synthesized by the introduction of polymolybdate. Both of complexes display three-dimensional "pillar-layer" frameworks based on bimetal-oxide inorganic layer. Good photocatalytic activities were observed for both complexes in the photo-decomposition of methyl orange solution under UV light irradiation. On the other hand, complex13possesses4-fold helical channel and is a water-stable MOF, which can sense anions with different geometries. The exchanged-products can be conveniently recognized by visual chroma. Moreover, the desolvated complex13 shows selective uptake of CO2over N2at ambient temperature.In chapter4, seven MOFs have been synthesized based on N/O multidentate ligands. The structural transformation between complexes16and17was achieved successfully by the pillar organic ligand under the same reaction conditions. The effect of synthetic conditions on the resulting structures have been discussed in detail. Moreover, the magnetic properties of16and17have been investigated and both of them show antiferromagnetic behaviour.In chapter5, four metal cluster-based MOFs have been obtained. The synthesis strategy of complex21opens up a new avenue for synthesizing metal cluster-based coordination frameworks. Furthermore, the gas adsorption and luminescent properties of complexes23and24have been systematically studied.In chapter6, a conclusion on this work is given.更多还原