本论文针对配位聚合物的构筑，围绕反应体系的pH、溶剂和配体的构型三个调控因素，开展了较系统的研究。选择不对称羧基配体和V型配体与不同的金属离子反应，构筑了35个配合物，解析了它们的结构，并研究了部分配合物的热稳定性和磁性质。通过结构分析和比较，归纳总结了反应体系的pH、溶剂和配体的构型对配合物的生成和结构的影响。具体内容如下：一．合成、表征了不对称羧酸配体4-羧基苯氧乙酸与过渡金属离子在不同pH下组装得到的8个配合物(1-8)。研究结果表明，反应体系的pH对含有不对称羧酸配体的配合物的形成产生了极为重要的影响。改变反应体系的pH，既影响配体的脱质子过程，又影响配体的配位模式。合理地调节反应体系的pH，可以实现金属/4-羧基苯氧乙酸配合物从单核分子(1，5)、一维链(3，4)、二维层(7)到三维网络结构(2，6，8)的构筑。合成了首例三重穿插后在对角线方向仍有客体占据一维孔道的CdSO4型结构的配合物(6)。测定了其中4个配合物(2，4，7，8)的磁性。二．选择4-羧基苯氧乙酸和4,4′-二羧基二苯基砜配体分别与金属离子在不同的溶剂中组装，得到9个配合物(9-17)，其中，配合物11和12是首次报道的4,4′-二羧基二苯基砜的配合物。结构分析表明不同构型的溶剂分子对调控配合物的结构起到非常独特的作用。这是设计合成微孔配位聚合物时可以利用的因素。除此之外，利用TG和变温X-射线粉末衍射实验证实微孔三维配合物15具有可逆的脱醇/重新醇化的性质，表明含有溶剂客体的配合物在设计合成动力学多孔的金属有机骨架方面有重要意义和应用前景。三．选择V型配体4,4′-二羧基二苯基砜和2,2-二(4-羧苯基)六氟丙烷分别与金属离子反应，合成了8个配合物(18-25)。利用4,4′-二羧基二苯基砜配体与金属离子形成V型构筑单元[M(dbsf)]进行配合物(18-21)的组装。其中，象配合物21的二重索烃型穿插结构仅有几例报道。2,2-二(4-羧苯基)六氟丙烷的配合物仅有一例报道。通过结构分析与对比可知，除了V型配体的刚柔性与对称性对配位聚合物的形成和结构及其功能有重要的影响外，连接配位点的基团组成及其构型也可导致形成的配位聚合物具有不同的结构和功能。V型配体构型的可微调性对于配合物的多样性和新颖结构的形成起到了重要作用。四．选用4,4′-二羧基二苯基砜配体与金属离子在溶剂热条件下反应，得到4个含有μ2-OH或μ3-OH基团的具有一维孔道的三维超分子配合物(26-29)。其中，配合物26-28含有由μ3-OH连接钴离子或镍离子产生的一维无机金属羟基链[Co3(μ3-OH)2]n或[Ni3(μ3-OH)2]n。配合物26具有亚铁磁行为，可能来自Co2和Co3二聚体单元和Co1离子的自旋态之间的铁磁作用及不同自旋Sd的反铁磁耦合作用。不同频率的交流磁化率数据表明配合物26可能存在自旋玻璃体或超顺磁体行为。零场交流磁化率数据表明配合物26具有单链磁体性质。在外加场下观测到的配合物26的双峰磁化率特点为有限尺寸效应提供了依据。另外，热重分析及X-射线粉末衍射研究表明：配合物26在脱溶剂/重新溶剂化过程中，骨架的完整性仍然可以保持。实验结果表明配合物26具有脱溶剂/重新溶剂化的可逆性质。

In this dissertation, we developed systematic research on the construction of coordination polymers based on three modulatory factors, pH of the reaction system, solvent and configuration of ligand. Thirty-five complexes were assembled by asymmetric carboxylic acid and V-shaped carboxylic acid ligand with different metal ions. These complexes were characterized by element analysis, IR and single crystal X-ray diffraction. For parts of them, thermal stabilities and magnetic properties were determined. By structural analysis and comparison of these complexes, the effect of pH, solvent and configuration of ligand on the formation and structure of complexes was studied.1. Under different pH, eight complexes (1-8) were synthesized by reaction of 4-carboxyphenoxy acetic acid (H2cpoa) with transitional metal ions. The crystal structures were characterized, showing that pH of the reaction system has significant influence on the formation and the structure of complexes containing asymmetric carboxylic acid ligands. Changing pH of the reaction system, would affect the deprotonation process and the coordination mode of ligand. Adjusting pH of the reaction system rationally, led to the diverse structures of M/H2cpoa complexes from mononuclear (1, 5), 1D chain (3, 4), 2D layer (7) to 3D network (2, 6, 8). Complex 6 was the first example of CdSO4-like framework possessing both triple interpenetration net and guest occupied channels along the diagonal direction. The magnetism of four (2, 4, 7, 8) of these complexes were observed.2. In different kinds of solvents, nine complexes (9-17) were synthesized by assembling of 4-carboxyphenoxy acetic acid (H2cpoa) and 4,4′-dicarboxybiphenyl sulfone (H2dbsf) ligand with metal ions, respectively. Complexes 11 and 12 were the first report of H2dbsf complexes. Structural analysis of these complexes displayed that solvents with distinct configurations have unique influence on modulating of the structure of complexes. This factor could be utilized in design and synthesis of microporous coordination polymers. Microporous 3D complex 15 possessed reversible desolvation/resolvation property, which can be confirmed by TG and PXRD. It shows that the complexes containing solvent guest is significant and promising in design and synthesis of dynamic porous metal-organic framework.3. Eight complexes (18-25) were obtained from reaction of V-shaped carboxylic acid ligands, 4,4′-dicarboxybiphenyl sulfone (H2dbsf) and 2,2-bis(4-carboxyphenyl)hexafluoropropane (H2bchf), with metal ions, respectively. Under hydro/solvothermal conditions, H2dbsf and M(II) ion form V-shaped building block [M(dbsf)]. Using these V-shaped building blocks, four complexes (18-21) were successfully assembled. Complex 21 is of a unusual catenane-like 2D layer structure. There is only one example of H2bchf complex in the document. From the structural analysis and comparison, we found that the rigidity, symmetry, along with composition and configuration of linker groups between coordination sites, have crucial effect on the formation, structure and function of the final products. The flexible configurations of V-shaped ligand bring important impact on the diversity and novelty of complexes.4. Under solvothermal conditions, four complexes (26-29) containing μ2-OH or μ3-OH groups were successfully obtained by the reaction of metal ions with 4,4′-dicarboxybiphenyl sulfone (H2dbsf). All of them form 3D supramolecular structure with 1D channel. In complexes 26-28, the μ3-OH groups connect cobalt/nickle ions to generate inorganic metal hydroxyl chain [M3(μ3-OH)2]n (M = Co, Ni). The T−T curve of complex 26 suggested a ferrimagnetic-like behavior, which can be suggested to arise from the AF coupling of the different spin Sd and the ferromagnetic coupling between dimer of Co2 and Co3 ions and S of Co1 ion. The ac magnetic susceptibility data of complex 26 indicate possible spin-glass or superparamagnetic behavior. The zero field ac magnetic susceptibility data suggest a single-chain magnet behavior of complex 26. This experimental observation of the double-peak feature in susceptibility in the applied field for 26 gives further evidence for the finite-size effects. In addition, the structural integrity of the framework was maintained in the desolvation/resolvation process of complex 26, which can be confirmed by TG and PXRD. These results show that complex 26 possesses reversible desolvation/resolvation property.