在水热/溶剂热合成中，许多因素影响配位聚合物结构及其性质。有机配体和金属离子作为配位聚合物的两个主要组成部分，对配合物的结构和性质起着决定性的作用。本论文选择不同的金属离子和不同有机配体进行反应，得到了17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、磁学性质和光物理性质。通过结构比较，分析了在配合物组装中金属离子、羧酸配体以及辅助配体的作用。1.用2,2′-二喹啉-4,4′-二羧酸二钾盐（K2L1）和邻菲啰啉（phen）配体与La(III)、Pr(III)、 Gd(III)、Tb(III)和Yb(III)离子反应，得到了5个配合物 [Ln(L1)1.5(phen)] (Ln = La, 1; Pr, 2)，[Ln2(L1)2(μ3-OH)2(H2O)2]•2H2O (Ln = Gd, 3; Tb, 4; Yb, 5)。前两个配合物同构，是以双核单元为结点组装成的二维层状结构；后三个配合物同构，是以四核单元为结点构筑的三维结构。在较高温度的条件下，重稀土离子容易水解，生成羟基簇配合物。从Ln(III)的配位数，Ln-N和Ln-O键键长以及配体的配位模式都能表现出镧系收缩效应。2. 在对苯二乙酸（H2L2）/phen体系中，分别加入Cu(II)、Zn(II)和Mn(II)离子，合成了3个配合物（[Cu(L2)(phen)]•2H2O，6；[Zn(L2)(phen)(H2O)]，7；[Mn(L2)0.5(phen)(H2O)3] (L2)0.5•(H2O)0.25，8）。在四氢呋喃-2,3,4,5-四羧酸（H4L3）/4bpy（4bpy = 4,4′-联吡啶）体系中，分别加入Mn(II)、Ni(II)、Zn(II)和Co(II)离子，合成了4个配合物 [Mn2(L3)(H2O)3]，9；[Ni2(H2L3)(4bpy)2(H2O)4]•H2O，10；[Zn4(L3)2(4bpy)2(H2O)2]•H2O，11；[Co2(L3)(H2O)]•0.17(CH3)2CHOH)•2.70(H2O)，12。通过结构比较可知，不同的金属离子及其配位数可以引起配体构型和配位模式的不同，从而得到不同结构和不同性质的配合物。在配合物6-8中，都存在着氢键和π-π堆积作用，导致了三维超分子的形成。3. 在苯基丁二酸（H2L4）/Cu(II)体系中，加入不同的辅助配体（phen、2bpy（2bpy = 2,2′-联吡啶）、4bpy和N3‾），得到了5个配合物 [Cu(L4)(phen)]•3H2O，13； [Cu(L4)(2bpy)]•0.5H2O，14；[Cu(L4)(2bpy)(H2O)]•3H2O，15；[Cu(L4)(4bpy)]•H2O，16；[Cu(L4)0.5(N3)(2bpy)]，17。结构比较表明，辅助配体的引入会导致配体构型的变化，从而产生不同结构的配合物。在配合物13和15中，还存在着三聚水分子，这对超分子的构筑起到了重要的作用。

There are many factors impacting the structure of complexes in hydro(solvo)thermal syntheses. Metal ion and organic ligand as two main parts of complexes play an important role in construction of complexes. In this dissertation, we synthesized 17 new complexes with different metal ions and ligands through hydro(solvo)thermal syntheses. These complexes were characterized by IR, element analysis and single crystal X-ray diffraction. The thermal stability, photophysical and magnetic properties of some complexes are discussed.1. Five new rare earth complexes [Ln(L1)1.5(phen)] (Ln = La, 1; Pr, 2)，[Ln2(L1)2(μ3-OH)2(H2O)2]•2H2O (Ln = Gd, 3; Tb, 4; Yb, 5) were assembled from 2,2′-biquinoline-4,4′-dicarboxylic acid, dipotassium salt (K2L1) and 1,10-phenanthroline (phen) with lanthanide ions. The different radii of lanthanide ions make the coordination numbers of lanthanide ions and the coordination modes of ligands changed, which can be attributed to lanthanide contraction effect. And the heavy lanthanide ions are liable to hydrolyse at higher temperature to form polynuclear hydroxo complexes.2. Seven transition metal complexes [Cu(L2)(phen)]•2H2O，6；[Zn(L2)(phen)(H2O)]，7；[Mn(L2)0.5(phen)(H2O)3](L2)0.5•(H2O)0.25，8; [Mn2(L3)(H2O)3]，9；[Ni2(H2L3)(4bpy)2 (H2O)4] •H2O，10；[Zn4(L3)2(4bpy)2(H2O)2]•H2O，11；[Co2(L3)(H2O)]•0.17(CH3)2CHOH)•2.70(H2O)，12 were synthesized by p-phenylenediacetic acid (H2L2)/phen and tetrahydrofuran-2,3,4,5-tetracarboxylic acid (H4L3)/4bpy (4,4′-bipyridine) with different transition metal ions. The effect of metal ions, especially their coordination geometries, on the construction of complexes is discussed.3. Five Cu(II) complexes with phenylsuccinic acid and different auxiliary ligands (phen、2bpy(2,2′-bipyridine)、N3‾ and 4bpy) [Cu(L4)(phen)]•3H2O，13； [Cu(L4)(2bpy)]•0.5H2O，14； [Cu(L4)(2bpy)(H2O)]•3H2O，15； [Cu(L4)(4bpy)]•H2O，16； [Cu(L4)0.5(N3)(2bpy)]，17 were synthesized. The different auxiliary ligands can effect the coordination modes of carboxylic acid, leading to different structure of complexes. And in complexes 13 and 15, lattice water molecules form trimers which link the 1-D chains via hydrogen bonds into 2-D supramolecular network.