【作者】 郭春燕；

【导师】 王尧宇；

【作者基本信息】 西北大学 ， 无机化学， 2009， 博士

【摘要】 近年来，基于金属-有机构筑模块的配位超分子化合物的晶体工程在化学、材料、医学及生物学等领域已迅速发展。这不仅因为这些化合物具有新颖、新奇、丰富多彩的结构，更重要的是它们在催化、电导、磁、主-客体化学、非线性光学、分子选择、气体吸附、生物活性等多个方面展现出潜在的、广泛的应用价值和前景。如今，运用晶体工程原理构建的配位聚合物、超分子化合物等高级新型有序结构分子聚集体己逐渐成为各个相关领域的研究热点之一。大量的研究事实表明，设计或选择合适的构筑单元，并运用理论预测与实验手段相结合的方法来构筑目标配合物，是获得具有预期结构和预期功能材料的首要任务，也是目前对研究者们最具挑战的一个环节。本论文在配位聚合物晶体工程组装原理的指导下，在分析了基于苯并咪唑类配体的配位化学及生物活性的领域研究状况的基础上，主要以配位超分子晶体学为基础，以含N多功能配体（含N二羧酸配体及设计合成的双苯并咪唑类配体）为配位基块，通过选择不同的过渡金属盐构筑具有特定功能的配位聚合物，并对其性质进行表征，特别是对其可能的生物活性进行了部分研究，以期获得具有结构新颖和功能特定的目标配合物。在一定的反应条件下，我们得到了九个具有新颖结构和特定功能的化合物，它们分别是：[pbb（Hpbb）₂]SO₄·8H₂O （1），[Zn（pbb）₂（H₂O）₄]（NO₃）₂·2C₂H₅OH·4H₂O （2），[Zn₂（pbb）₂（μ-OH）（μ-OAc）]（OAc）₂·7H₂O（3），[Cd（pbb）₂（H₂O）₄]（NO₃）₂·2C₂H₅OH·4H₂O（4），[Cu（pbb）₂（H₂O）₄]Cl₂·2DMF-6H₂O （5），[Co（pbb）₂（H₂O）₄]（NO₃）₂·H₂O （6），[Ni（pbb）₂（H₂O）₄]（NO₃）₂（7），[Ag₂（bpp）₂（H₂O）]·pydc·7H₂O（8），Cd（pzdc）（μ₂-H₂O）（H₂O）（9）。首先，对所合成的化合物进行了X-射线单晶结构测试和分析，运用元素分析、红外光谱、X-射线粉末衍射、热分析、荧光光谱等技术进行了谱学表征和性能研究。结果表明，配体的几何构型及金属元素的差异对配合物的结构影响很大。不同的Zn^Ⅱ盐导致了不同的化合物1、2、3的产生。1中椅式构象（H₂O）₆环外对称地悬挂一对三聚水（H₂O）₃构成了独特的（H₂O）₁₂簇；借助强烈的π-π堆积作用形成的2的三维分子堆积结构中包含了一维开放隧道，阴离子恰包裹其间；双核结构3中，游离水、配位水及-OH通过氢键共同构筑了一个八元冠状环。在配合物4和5中，阴离子分别参与一维氢键梯状链的构筑。在5中，三种来源不同的氧构筑了十二元O-H…O氢键单元。6和7中有机配体呈规则排列，π-π堆积作用显著。在5和6中，金属原子排列有序，在空间分别呈（3,6）和（4,4）排列。8中（H₂O）₄环外对称地悬挂一对（H₂O）₃水簇及一对水单体构成了中心对称的（H₂O）₁₂簇。对于三维配合物9，四元环Cd₂O₂簇连接成1D环状链，而金属Cd构成了一维内消旋金属螺旋链结构。所有这些新颖有趣结构的出现都大大丰富了配位化学及超分子化学的内涵。其次，以这些在生命体系中具有潜在应用前景的苯并咪唑类功能配合物为研究对象，运用抑菌圈法及微量量热技术研究了这些配合物对所选菌种的无机生物化学效应。抑菌圈法研究结果表明，配体pbb及其配位化合物2-7对所测菌种是有抑制作用的且具有选择性。微量热法研究结果表明，37℃时pbb及其配位化合物2-7对所测菌种E.coli是有抑制作用的，且最为重要的是，和金属离子配位后pbb的抑菌活性得到了明显的改善。这些初步的研究工作，为pbb及其配合物在医药、生物、化学等领域的潜在应用提供了初步的重要的理论信息，具有一定的现实指导性意义。更多还原

【Abstract】 The crystal engineering of supramolecular architectures based on metal and organic building blocks has been rapidly expanding in recent years in chemistry, materials, medicals and biology areas owing to not only their novel topologies and intriguing architectures but also their potential applications in catalysis, electrical conductivity, magnetism, host-guest chemistry, nonlinear optics, molecular recognition, gas adsorption and biological activity. Today, in the realm of supramolecular chemistry, great interest has been focused on the crystal engineering of coordination frameworks by use of the principles of self-assembly. It is demonstrated that considerate designing or selecting rational building block through appropriative assembly strategy should be the key in constructing target polymers and also a stubborn challenging work for scientists.In this research, with the aim of obtaining new materials with beautiful architecture and excellent physical properties, we selected multi-functional N-containing ligands （N-containing dicarboxylate ligands and benzimidazolic ligand） as building blocks to construct coordination polymers with selected transition metal ions guided by assembly principle of coordination polymers crystal engineering after the relative research background is considered. Under different reaction condition, nine coordination polymers have been synthesized. They are listed as follows: [pbb（Hpbb）₂]SO₄·8H₂O （1）, [Zn（pbb）₂（H₂O）₄]（NO₃）₂·2C₂H₅OH·4H₂O （2）, [Zn₂（pbb）₂（μ-OH）（μ-OAc）]（OAc）₂·7H₂O （3）, [Cd（pbb）₂（H₂O）₄]（NO₃）₂·2C₂H₅OH·4H₂O （4）, [Cu（pbb）₂（H₂O）₄]Cl₂·2DMF·6H₂O （5）, [Co（pbb）₂（H₂O）₄]（NO₃）₂H₂O （6）, [Ni（pbb）₂（H₂O）₄]（NO₃）₂ （7）, [Ag₂（bpp）₂（H₂O）]·pydc·7H₂O （8）, Cd（pzdc）（μ₂-H₂O）（H₂O） （9）.These polymers have been characterized by X-ray single crystal diffraction analysis, elemental analysis, IR spectra, XRPD analysis, thermal analysis and fluorescence spectroscopy to investigate the spectroscopy characters and properties. The results revealed that the conformation of the ligands play an important role in the structure of complexes. Different Zn^Ⅱsalts induced the creation of different compound complexes 1, 2 and 3. A unusual （H₂O）₁₂ cluster constructed by a chair conformation （H₂O）₆ ring core with a pair of （H₂O）₃ is observed in 1; with the help of strong aromaticπ-πinteractions, 2 presents 3D supramolecular structures involving 1D open channels encapsulating NO₃^- ions; a eight-membered crown-like rings in 3 are formed via hydrogen bonds between coordinated water, free water molecules and -OH. In 4 and 5, anions participate in the formation of 1D latter-like chain via hydrogen bonds, respectively. Three kinds of oxygen atoms construct a twelve-membered unit by O-H…O hydrogen bonds in 5. The organic blocks are arranged regularly byπ-πstacking interactions in 6 and 7. A centre-symmetric （H₂O）₁₂ cluster comprising one （H₂O）₄ ring core and two additional （H₂O）₃ and two dangling monmeric water in 8 is rather unusual. In 3D complex 9, 1D ring-like chain is formed by four-membered Cd₂O₂ units. All of the new and interesting structures contribute to the richness of coordination chemistry and supramolecular chemistry.Additionally, the antimicrobial activities of pbb and 2-7 were investigated by the inhibitory zone test method and microcalorimetry. The results from the inhibitory zone test method indicate that pbb and 2-7 have selective inhibition property for the testing strains. The results from microcalorimetry reveal that pbb and 2-7 can inhibit the growth of E. coli at 37℃. Importantly, the presence of metal ions has improved clearly antibacterial activity of ligand pbb. We believe that this work may contribute basic information to the further application of pbb and its complexes in chemistry, medicals and biology fields.更多还原