【作者】 黄泳权；

【导师】 程鹏； Jeffrey R.Long；

【作者基本信息】 南开大学 ， 无机化学， 2009， 博士

【摘要】 金属-有机骨架（Metal-Organic Frameworks,MOFs）材料是一类具有广阔应用前景的新型固体材料,正迅速发展并成为能源、材料和生命科学交叉领域中的研究热点。本论文从金属有机骨架材料的新颖结构和功能性出发,通过选择功能性的金属中心和含N的唑类有机配体,设计合成了一系列多功能骨架结构的晶体材料,解析了13个配合物的单晶结构,利用元素分析、红外光谱、变温磁化率、荧光光谱、氮气和氢气吸附等手段对这些配合物进行了表征和性质研究。本论文的主要工作如下:1.利用双三唑4,4’-bis-1,2,4-triazole（btr）配体与Mn（Ⅱ）合成了1个新颖的具有较强反铁磁作用的二维金属-有机骨架材料。2.为了得到更多关于超分子构筑体系和双三唑btr配合物的信息,通过调控阴离子和金属中心的变化,设计合成了8个以Cu（Ⅱ）和Cd（Ⅱ）为中心的双三唑MOFs材料,系统地讨论了btr特殊的桥联方式,阴离子和金属中心在构筑结构骨架中的作用。得到三唑金属化合物中首例btr配体在单一体系中以μ₃-和μ₂-桥联配位的化合物。通过Cu（Ⅱ）系列化合物的变温磁化率测定揭示了二价铜离子的反铁磁相互作用。3.利用吡啶基双三唑2,6-di-（4-triazolyl）pyridine（dtp）配体与Cd（Ⅱ）制备了1个新颖的三维孔洞金属-有机骨架材料,其荧光的发射可以在紫外光区与可见光区可逆的进行,仅仅通过调节孔洞中的客体水分子数目可达轻易调控的目的,而客体水分子的自由进出不会引起整体孔洞结构的坍塌,是一个很有潜力的发光材料。4.选用4-苯甲酸四唑双功能配体4-（2H-tetrazol-5-yl）benzoic acid（4-H₂TzB）分别与Mn（Ⅱ）和Mg（Ⅱ）合成了3个结构新颖、具有高对称性的微孔金属-有机骨架材料,对氮气和氢气的吸附做了尝试性的测试,此内容是本人在联合培养期间于美国加州大学伯克利分校Jeffrey.R.Long教授的科研组完成。更多还原

【Abstract】 With rapid development and playing a key role in energy, materials and life sciences, Metal-Organic Frameworks （MOFs） are one such important type of solid-state materials with great prospects of practical applications. According to the principle of molecular design, thirteen novel MOFs based on the triazolate and tetrazolate ligands have been synthesized and determined by X-ray single crystal diffraction analysis. These complexes have been characterized by elemental analysis, IR, variable temperature magnetic susceptibility measurements, fluorescence and N₂, H₂ absorption measurements. The main contributions in this work are blow:1. A novel 2D Mn（II） MOF with 4,4’-bis-1,2,4-triazole （btr） has been obtained. Strong antiferromagnetic interactions between Mn（II） ions are observed.2. To obtain more information on supramolecular architecture construction and btr-metal coordinated structures, eight complexes of btr and M（II） （M = Cu and Cd） have been successfully synthesized, one of which is the first example of theμ₃- andμ₂-btr simultaneity in a single system in triazole-metal complexes. The variety of dimensionalities based on the tuning of different anions and metal centers were detailed discussed. Variable-temperature magnetic susceptibility studies on the Cu（II） compounds reveal the overall antiferromagnetic behaviors.3. A novel 3D porous MOF built with 2,6-di-（4-triazolyl）pyridine （dtp） and Cd（II） has been synthesized and characterized as a promising luminescent material that can give tunable emissions between UV and visible wavelengths by controlling the number of the guest molecules.4. Using 4-（2H-tetrazol-5-yl）benzoic acid （4-H₂TzB）, three of Mn（II） and Mg（II） novel 3D porous MOFs have been synthesized. The trial N₂, H₂ absorption isotherms have been determined. This part of research was supervised by Prof. Jeffrey. R. Long in University of California, Berkeley, USA, as a visiting student researcher.更多还原