【作者】 金首文；

【导师】 陈万芝； 王彦广；

【作者基本信息】 浙江大学 ， 有机化学， 2007， 博士

【摘要】 由于配位聚合物具有多样的结构及其具有光、电、磁等性质，加上它在多个领域如分子识别、催化、分离、分子器件等方面具有潜在的用途，因此具有特殊拓扑结构和特殊性质的配位聚合物是当今的研究热点。本文通过一些简单易得的含氮配体与过渡金属配位得到了一系列具有不同维数及拓扑结构的配合物，并通过元素分析，红外，X-光单晶衍射表征。某些化合物具有强的荧光及良好的热稳定性能。本文共分五章：第一章介绍了构筑配位聚合物的一些常见方法及功能配合物的一些应用前景。第二章研究了在钯催化剂及易得的三苯基膦辅助配体作用下卤代萘啶与含氮杂环的C-N偶联反应。催化反应比较容易进行，分离简单，以中等收率得到了8个新的杂原子取代的萘啶衍生物。另外利用部分1，8-萘啶衍生物进行了其配位化学行为的研究。发现萘啶衍生物可以以双齿桥联及单齿方式与一个或两个金属配位，而且得到的配合物进一步通过各种各样的分子内和分子间弱作用力（Ag-pπ，Ag-Ag作用，静电作用（卤键）及氢键）形成多维超分子结构。第三章本章中我们用简单的方法成功的合成了六个新的六氯化锡与咪唑阳离子的配合物。这些化合物均通过各种各样的弱作用力形成三维结构的超分子。研究发现超分子的结构特征与配体的大小、对称性及阳离子所带的电荷数目有关。由于咪唑衍生物容易制备，其结构容易调节改变，所得配合物热稳定性好，因此可以通过改变阳离子得到具有新颖结构和功能的有机-无机杂化材料。第四章由于柔性配体具有可变的配位构型，利用它与过渡金属组装的研究相对较少。我们利用易得的柔性配体合成了十一个新的配合物，它们的结构互不相同。结果表明利用柔性的桥联咪唑与过渡金属组装可以得到1-3维的超分子聚集体。[Zn（nba）₂L⁶]（21）（L⁶=1，4-咪唑丁烷，nba=对硝基苯甲酸根）、Ni（L⁶）（hba）₂（MeOH）₂]·2MeOH （22） （hba=对羟基苯甲酸根）和[Zn（hba）₂（L⁹）]₂·EtOH·3H₂O（23）（L⁹=1，1′-苯并咪唑甲烷）为一维之字链结构，L⁶及L⁹起到桥联的作用分别将[Zn（nba）₂]和[Ni（hba）₂（MeOH）₂]单元连接起来，由于金属原子的配位性能及配体中烷基桥的长度不同，这三个化合物的空间排列是互不相同的。[Mn（L⁷）₂（H₂O）₂]Cl₂·2H₂O（24）（L⁷=1，1′-咪唑甲烷）、[Fe（L⁷）₂（NCS）₂·2H₂O]（25）和[Co（L⁷）₂（H₂O）₂]（sal）₂·4H₂O（26）（sal=水杨酸根）为一维双链结构。配合物[Cd（L⁶）_1.5（NCS）₂]（27），[Cd（L⁶）₂（NO₃）₂]（28），(Cd（L⁶）₂（tos）₂]（29）（tos=对甲苯磺酸根），[Co₂（L⁶）₄（NCS）₄]·4MeOH（30）为具何（4，4）拓扑结构的二维网格。[Ni（L⁶）₃]（NO₃）₂（31）具有阳离子索烃结构，不参与配位的硝酸根离子处于由互穿网络形成的三角形通道中。本章研究了不同反离子及反离子的不同配位模式对超分子结构的影响，而不同的中心金属由于其配位数目的不同，得到的配合物的结构也不相同。在镉的配合物28中，硝酸根以单齿方式配位，形成的配合物为具有（4，4）拓扑结构的二维网格，而在镍的配合物31中硝酸根作为不参与配位的反离子，因此得到具有通道的三维结构。本章以硫氰酸根为负离子的3个配合物（25、27和30），其结构互不相同。另外配体桥的长短对于具有方格结构的配合物方格的大小具有重要的影响。上述配合物热稳定性好，d¹⁰金属（Zn和Cd）的配合物（21，23，27-29）室温下具有强的荧光，因此这些超分子配合物有望成为新的功能材料。第五章本章合成了一系列具有不同结构的Mn（Ⅱ），Cu（Ⅱ），Co（Ⅱ），Ni（Ⅱ），Zn（Ⅱ）和Cd（Ⅱ）的配合物，通过X光衍射，红外光谱及元素分析对其进行了表征，研究了它们的热稳定性能及发光性能。由于二酸的链长和刚性不同，二酸的配位模式也不同。二酸与桥联咪唑一起与过渡金属组装得到了各种各样结构的配合物。这些配合物具有一维单链，梯状，二维薄片结构及三维网状结构。脂肪及芳香二酸可以采取螯合的μ₂，桥联的μ₂及螯合与桥联同时存在的μ₃及以双齿桥联等模式参与配位，或者作为不参与配位的反离子存在。中心金属离子根据辅助配体的不同而以N₂O₄，N₄O₂，N₂O₃，N₃O₃和N₂O₅等模式与配体配位。L⁶和L⁷作为双齿配体参与配位，结果表明利用柔性的桥联咪唑与柔（刚性）性的二酸作为砌块可以组装得到不同刚状结构的配合物，而且利用柔性配体不一定会得到三维互穿结构。在这些配合物中羧酸均参与形成氢键作用，羧酸还可以起到模板作用在它周围固定一定的水簇，这些水簇围绕着羧酸形成各种各样的水环和氧环结构，另外羧酸固定水分子的个数与羧酸在空间伸展的大小有关。[zn（imc）（L⁷）]·H₂O（43）（imc=亚氨基二乙酸根）和[Cd（L⁶）（male）]-H₂O（45）（male=马来酸根）具有较好的热稳定性能，而且在室温下发射出强的蓝光，因此这两个超分子配合物有望成为新的蓝光材料。更多还原

【Abstract】 Coordination polymers have recently attracted considerable interest, owing to their versatile framework topologies as well as their special properties, such as optical, electrical and magnetism properties. In addition, these materials may have many potential utilities in molecular recognition, catalysis, separation and molecular devices, so many researchers show great interest in studying complexes having new topological structures and special properties.In this thesis, by combining the ligands with transition metals we prepared a series of transition metal complexes of different dimensions and novel topological structures and these complexes were characterized through elemental analysis, IR, and X-ray diffraction analyses. Some compounds show strong photoluminescence and good thermal stability. The thesis consists of five chapters:In Chapter 1, we introduced the strategies of how to build coordination polymers and their potential utilities in material science.In Chapter 2, eight novel heteroaryl functionalized 1, 8-naphthyridine derivatives have been prepared by Pd（OAc）₂/PPh₃ catalyzed amination of chloronaphthyridine. The Pd-catalyzed reactions progress smoothly, the separation procedure was simple and yields are moderate. The coordination behavior of several 1, 8-naphthyridine derivatives was investigated, and it was found that 1, 8-naphthyridine derivatives can act as bidentate bridge ligands, and monodentate ligands to bind one or two metals. The transition metal coordination complexes of 1, 8-naphthyridine derivatives can form multi-dimensional supramolecules through various inter- and intramolecular weak bonds such as Ag…Ag interaction, Ag…pπinteraction, halogen bonds and hydrogen bonds.In Chapter 3, we have synthesized six new imidazolium hexachlorostannate compounds by simple methods. These compounds exhibit three dimensional layer structures for the presence of interand intramolecular weak interactions such as hydrogen bonds,π-πstacking. The structure motifs of these complexes depend on the size, symmetry, and the charge number of the organic cations. Because the imidazole derivatives are easily prepared and the structures can be easily tuned, it is believed that the organic-inorganic tin compounds with novel structures and functionalities can be expected by variation of the organic cations. In addition the compounds were thermally stable, and they may be used as novel organic-inorganic hybrid materials.In Chapter 4, we prepared eleven novel complexes from self-assembly of the corresponding metal salts with flexible ligands and their structures were fully characterized by IR, and x-ray diffraction analyses. The flexible ligands may adopt various conformations when coordinating with transition metals, and thus there were little studies on the construction of coordination polymers by using flexible ligands. One to three dimensional supramolecular aggregates were formed by reacting of alkyl bridged diimidazole derivatives with transition metals. X-ray diffraction analyses revealed that complexes [Zn（nba）₂L⁶] （21） （L⁶ = 1, 4-bis（N-imidazolyl）butane, nba = p-nitrobenzoate）, Ni（L⁶）（hba）₂（MeOH）₂]·2MeOH （22） （hba = p-hydroxybenzoate）, and [Zn（hba）₂（L⁹）]₂·EtOH·3H₂O （23） （L⁹ = bis（N-benzimidazolyl）methane） have 1D zigzag chain structure in which [Zn（nba）₂], and [Ni（hba）₂（MeOH）₂] units are held together by L⁶ or L⁹ ligands. Complexes [Mn（L⁷）₂（H₂O）₂]Cl₂·2H₂O （24） （L⁷= bis（N-imidazolyl）methane）, [Fe（L⁷）₂（NCS）₂·2H₂O] （25）, and [Co（L⁷）₂（H₂O）₂]（sal）₂·4H₂O （26） （sal = salicylate） exhibit 1D double-stranded chain structures resulted from doubly bridged [Mn（L⁷）2（H₂O）₂], [Fe（NCS）₂], and [Co（L⁷）₂（H₂O）₂] cations, respectively. Complexes [Cd（L⁶）_1.5（NCS）₂] （27）, [Cd（L⁶）₂（NO₃）₂] （28）, [Cd（L⁶）₂（tos）₂] （29） （tos=p-tolylsulfonate）, and [Co₂（L⁶）₄（NCS）₄]·4MeOH （30） have 2D grid network structures with （4, 4） topology. Complex 31 is a cationic polycatenane, and the nitrate anions occupy the triangular channels formed by the interpenetrated networks.The Cd complex 28 has a （4, 4） topology network structure in which the nitrate anions coordinated as monodentate ligands, whereas nickel complex 31 displays a three dimensional interpenetrated network structure with the nitrate as counter anion. For compounds 25, 27, and 30, the NCS^- anions coordinated to the central metals via different mode, thus different structural compounds were formed. Complexes 27-30 with （4, 4） topology 2D grid network structures have different grids dimensions which is due to the different spacer lengths between the donating atoms. All these complexes are thermally stable. In the solid state all the d¹⁰ metal complexes （Zn and Cd） display strong emissions at room temperature, and thus these compounds may be used as candidates for novel functional material.In chapter 5, we used two structurally related flexible imidazolyl ligands （L⁶）, and （L⁷） to react with Mn（Ⅱ）, Cu（Ⅱ）, Ni（Ⅱ）, Zn（Ⅱ）, Cd（Ⅱ）, and Co（Ⅱ） salts of aliphatic/aromatic dicarboxylic acids, we get a number of novel metal-organic coordination architectures. The complexes were characterized through X-ray diffraction, elemental analysis, and IR spectra. The thermal and emission properties were also studied. The different coordination modes of dicarboxylate anions due to their chain length, rigidity and diimidazolyl functionality lead to a wide range of different coordination structures. The coordination polymers exhibit 1D single chain, ladder, 2D sheet and 3D network structures. The aliphatic and aromatic dicarboxylates can adopt chelatingμ₂, bridgingμ₂, and chelating-bridgingμ₃ coordination modes, or act as uncoordinated counter anions. L⁶, and L⁷ act as bidentate bridging ligands. The central metal ions are coordinated in N₂O₄, N⁴O², N₃O₃, N₂O₃. and N₂O₅ fashions depending on the ancillary ligands. The structure motifs tell that we can get different network by utilizing flexible divergent diimine ligands and dicarboxylate as building block. In addition, flexible ligands assembling with transition metals did not definitely lead to the formation of 3D supermolecules. In all these complexes, dicarboxylate auxiliary ligands participate in hydrogen bonds, through these hydrogen bonds the supermolecular structures were stabilized. When dicarboxylate auxiliary ligands act as uncoordinated counteranions, they function as templating agents fixing water molecules around them, the number of water molecules around the dicarboxylates relies on the span of the dicarboxylate. The water molecules around the dicarboxylate anions form various water and oxygen rings. Complexes 43 （[Zn（imc）（L⁷）]·H₂O, imc=iminodiacetate） and 45 （[Cd（L⁶）（male）]·H₂O, male=maleate） were thermally inert, and in the solid state they have strong blue emissions at room temperature, these two compounds may be used as excellent candidates of blue-fluorescent materials.更多还原