【作者】 李程鹏；

【导师】 田宜灵； 杜淼；

【作者基本信息】 天津大学 ， 物理化学， 2009， 博士

【摘要】 本论文运用晶体工程的经验和构筑策略,选用了含有取代芳香羧酸有机配体,并以之为构筑块在适当的条件下与金属离子组装制备出具有新颖网络结构的金属基超分子配合物。重点研究了这类配合物的合成条件,其取代基团对配体构型的定向调控,分析网络拓扑形成的规律以及辅助配体对于整个结构的影响等方面。全文共分为五章:第一章首先介绍了此项工作的研究背景,重点介绍了基于芳香羧酸类配体的配位聚合物的研究进展及其在吸附和催化等方面的应用;并在此基础上提出了本论文选题的依据、目的及所取得的进展。第二章我们首次利用2,3,5,6-四溴代对苯二甲酸(H2TBTA)与ZnII, CoII, AgI和PbII反应成功得到五个从一维到三维的配位聚合物,包括一维聚合链,二维kgd,二维CdCl2,三维多节点的(4~2.8~4)(4~3)2(4~4.6~4.8~2)2(4~5.6~3.8~2)2(4~6.6~3.8)2复杂拓扑结构。晶体结构研究表明在与ZnII的组装过程中,溶剂分子所体现出来的结构导向和模板化效应对于形成的配位聚合物的结构产生了非常大的影响。第三章在H2TBTA的基础上,我们首次将共配体2,5-双(4-吡啶)-1,3,4-噁二唑(4-bpo)及其3-吡啶衍生物(3-bpo)引入到金属离子(CoII, NiII, CuII, ZnII, AgI, CdII和PbII)的超分子组装体系中,得到了结构各异的金属基超分子配合物6-17。对于另一种衍生物H2BTA与金属ZnII和CdII在3-bpo的存在下所形成的配合物18和19的结构分析表明,由于取代基空间位阻的减弱,对于羧基的配位能力也有一定影响,进而对最终形成的超分子网络产生了显著的结构差异。第四章为了进一步研究共配体对于取代的芳香羧酸配体所形成的配合物网络结构的影响,我们引入了5-磺酸基代间苯二甲酸(H3SIP),将之与3-/4-bpo和金属离子反应得到20?27。其中,在H3SIP, CdII以及3-/4-bpo的反应体系中通过调节反应体系的pH值,不仅可以对其中参与配位的3-bpo配体的构型起到了调控效应,还对于最终形成结构网络的维度有决定性的影响。第五章设计了具有配位惰性基团取代的烟酸衍生物,5-溴代烟酸(5-HBN)及其衍生物5-溴代烟酸氮氧化合物(5-HBNO),并将之与CoII, CuII, ZnII和CdII进行了自组装,分别得到了八个结构新颖的配合物28?35,其中包括未报道过的(3,5)-连接和(3,6)-连接聚合网络结构。另外,在CuII(28和29)和CdII(30?32)配合聚合物中,溶剂分子的选用对于最终的配位聚合网络产生了重要的结构导向作用和模板化效应。更多还原

【Abstract】 On the basis of the policy of crystal engineering and constructing strategy, a va-riety of substituted aromatic carboxylic acids were chosen as the building blocks to assembly with metal ions to afford novel topological metallosupramolecular com-plexes. The key points of our research are on the emphasis of synthetic methodology of interesting metallosupramolecular complexes, directional regulation of ligation fa-shion from substituents to ligand, analysis of assembly discipline of topological net-work, and impact of co-ligand to the resultant framework. This thesis consists of five chapters.In chapter 1, the recent research progress of coordination polymers based on aromatic carboxylates was represented and their useful properties on catalysis ability and microporosity were also demonstrated. Then the research significance and main conclusion of this thesis were summarized.In chapter 2, five novel ZnII, CoII, AgI and PbII coordination polymers based on a versatile building block 2,3,5,6-tetrabromoterephthalic acid (H2TBTA) have been successfully assembled, including 1-D polymeric chain motif, 2-D kgd and CdCl2, as well as 3-D (42.84)(43)2(44.64.82)2(45.63.82)2(46.63.8)2 network. In these complexes, all the carboxyl groups were appeared as the deprotonized fashion in a vertical pattern to the central aromatic ring. Single crystal X-ray diffraction studies revealed that mod-ulation of solvent choice made the significant impact on the resultant ZnII networks in the structural direction and template effect function.In chapter 3, on the basis of H2TBTA, by employment of 2,5-bi(4-pyridyl)- 1,3,4-oxadiazole (4-bpo) and its 3-N-donor analogue (3-bpo) into the supramolecular assembly system with metal ions (CoII, NiII, CuII, ZnII, AgI, CdII and PbII), complexes 6-17 featured a variety of interesting structures. Furthermore, analysis of another de-rivative H2BTA related complexes 18 and 19 revealed that the discrepancy of the re-sultant networks may arise from the spatial effect distinction of the substituent at-tached to the aromatic ring and then the coordination modes of the carboxylates.In chapter 4, in order to further study the influence of co-ligands upon the coor-dination network from substituted aromatic carboxylates, 5-sulfoisophthalic acid (5-H3SIP) was utilized to react with metal ions, in virtue of 3-/4-bpo, to afford com-plexes 20?27. Notably, in the self-assembly of 5-H3SIP, CdII and 3-/4-bpo, pH value played the vital role not only to the regulated configuration of 3-bpo, but also to the structural dimension of the resultant frameworks.In chapter 5, 5-bromonicotinic acid (5-BN) and 5-bromonicotinic acid N-oxide (5-HBNO), derivatives of nicotinic acid with 5-Br substituent, were employed to react with CoII, CuII, ZnII and CdII to afford eight novel complexes 28?35, including two unprecedented architectures with (3,5)- and (3,6)-connected net topology. In the po-lymers 28?29 and 30?32, manipulation of specific solvents shows a significant struc-tural direction and template effect to the resultant frameworks, respectively.更多还原