【作者】 杨玉蓉；

【导师】 施继成；

【作者基本信息】 福建师范大学 ， 无机化学， 2009， 硕士

【摘要】 配位聚合物因其在不对称催化、气体吸附、非线性光学以及磁性材料等方面的潜在应用价值,而成为近年来化学研究的热点领域之一。因此,研究功能有机配体与金属离子的定向组装规律以及对配位聚合物的结构与性质之间关系的探索,对于超分子化学和材料化学的发展具有重要的意义。由于这类由金属离子和有机配体组装的配位聚合物的结构特点及性能很大程度上取决于有机配体的结构。因此,合理选择或者是设计合成有机配体是有效合成配位聚合物的重点之一。L-酒石酸是一种易得的、具有手性的化合物,其羧酸根及羟基都是易参与配位的基团,因此以L-酒石酸为原料,合成了几种有机配体,并对它们进行了表征。通过水热合成技术,用（4R,5R）-2,2-二-甲基-N,N’-二（吡啶-4-基）-1,3-二氧戊环-4,5-二甲酰胺(C₁₇H₁₈O₄N₄)与镉盐合成了新颖手性配位聚合物[Cd₆（C₄H₂O₆）₆]·CH₃OH（1）;用2,3-O-异丙叉基-L-酒石酸钠（Na₂C₇H₈O₆）、异烟酸与银盐及铜盐分别合成了配位聚合物[Ag（C₆H₄O₂）（C₆H₅O₂）]·4H₂O（2）和[Cu（C₆H₄NO₂）₂]·4H₂O（3）。通过IR、元素分析和单晶X射线衍射对以上三种晶体进行了表征。配位聚合物（1）保留了配体L-酒石酸的手性特征,属于正交晶系,C222₁手性空间群。配位聚合物（1）和（3）均为单斜晶系,P（?）空间群,两种化合物的结构中都存在复杂的氢键作用。通过荧光测试发现配位聚合物（1）的荧光强度是配体的三倍,配位聚合物（2）的荧光发光强度也比配体的要强。解释为配体与金属离子的配位作用引起了配体到金属离子或金属离子到配体的电荷转移（LMCT）,从而增强了配位聚合物的发光强度。配位聚合物（3）的荧光最大发射峰较配体发生了蓝移,发射峰变宽。更多还原

【Abstract】 Recently, because of its potential applications in some fields, such as absorption, selective catalysis, nonlinear optical and magnetic materials, the coordination polymer has became one of the particularly important and hot research subjects. Therefore, it is of great importance for the development of supramolecular chemisty and material science to explore the assembly of functional organic ligand with metal ion and to investigate the relationship of the structure and property. It is well known that, the structural characteristics and properties of the coordination polymers depend heavily on the organic ligand, hence, the selection of the organic ligand is key to synthesize of coordination polymers.In the present investigation, several chiral ligand were designed and synthesized using available L-tartaric acid as the start material, and they were characterized by IR, MS, ¹H NMR. Assembly of N,N-bis-（4-pyridyl）-（4R,5R）-2,2-dimethyl-[1,3]-dioxolane-4,5-dicarboxamide with Cd（Ⅱ） ion using the hydrothermal technique afforded the novel chiral complex: [Cd₆(C₄H₂O₆]·CH₃OH （1）; then we using 2,3-O-isopropylidene-L-tartrate sodium and isonicotinic acid to assemble with transition metals （Ag or Cu）, which obtained two coordination polymers: [Ag（C₆H₄O₂）（C₆H₅O₂）]·4H₂O （2） and [Cu（C₆H₄N-O₂）₂]·4H₂O（3）The compounds were characterized by IR, elemental analyses, and single crystal X-ray diffraction. The compound （1） belongs to orthorhombic system, C222₁ chiral space group while the compound （1） and （2） belong to monoclinic system, P（?） space group, and we also found there are serveral hydrogen bonding in both compound （1） and compound （2）.Moreover, the fluorescence intensity of these compounds was also determined, and the results showed that the fluorescent intensity of the coordination polymer （1） and （2） were stronger than its ligand, respectively. Especially, coordination polymer （1） was found to be the most efficient molecule, which its fluorescent intensity was three times potent than the corresponding ligand. It is believed that the coordination of metal ion with orgnic ligand enhanced the fluorescence intensity. Furthermore, by analogy with the emission spectrum of compound （3） and isonicotinic acid, the conclusion was obtained that the assembly of isonicotinic acid with transition metals （Cu） make the emission spectrum produce a broadband and peak value arise an obvious blue shife.更多还原