【作者】 徐广娟；

【导师】 颜力楷； 苏忠民；

【作者基本信息】 东北师范大学 ， 物理化学， 2010， 硕士

【摘要】 配位聚合物因其独特的结构可剪裁性、多样的拓扑结构以及在气体存储、催化、磁性等领域的潜在应用受到了人们的广泛关注。依据分子工程学原理,通过选择特定金属离子和适当的有机配体,可以在一定程度上实现新型功能材料的定向设计与合成。本论文利用三种新型吡啶羧酸类配体(3,5-二(吡啶-4-甲氧基)苯甲酸(HL1),3,4-二(吡啶-4-甲氧基)苯甲酸(HL2)和3,5-二(吡啶-3-甲氧基)苯甲酸)(HL3),在水热条件下得到了10种配合物。研究表明:配合物的结构受诸多因素的影响,如金属离子的配位模式与配位数、配体自身的性质、反应的酸碱度、溶剂及辅助配体等。此外,研究了部分配合物的固态荧光和热稳定性质。具体内容如下:1、合成了新型的吡啶羧酸类配体3,5-二(吡啶-4-甲氧基)苯甲酸(HL1),3,4-二(吡啶-4-甲氧基)苯甲酸(HL2)和3,5-二(吡啶-3-甲氧基)苯甲酸(HL3),其和刚性配体苯二酸与双核(或三核)金属镉簇次级结构单元结合形成三个新颖的(3,8)-连接配合物:[Cd2(L1)2(1,3-bdc)] (1), [Cd2(L2)2(1,4-bdc)]·3H2O (2), [Cd3(L3)2(1,3-bdc)2] (3)。配合物1和3呈现出新颖的(3,8)-连接网络结构,其拓扑是新颖的并且未曾被报道过,其拓扑符号分别为(42·6)2(44·622·82)和(42·5)2(44·56·610·75·82·9);配合物2的拓扑符号为(43)2(46·618·84),属于tfz-d型网络。2、利用3,5-二(吡啶-3-甲氧基)苯甲酸(HL3)与过渡金属在水热条件下反应,成功得到五个具有二维结构的配合物:[Cd(L3)2]·H2O (4), [Zn(L3)2] (5), [Co(L3)2] (6), [Ni(L3)2] (7), [Cu2(L3)2]·3H2O (8)。配合物4是一个(3,4)-连接的二维层状结构,其拓扑符号为(63)(66)。配合物5~7是异质同构体,在其结构中包含有Zn-L3配体的44元环状结构,这种环状结构形成单手性的螺旋层,由于层与层之间的手性相反,所以,配合物的整体是一个非手性结构。其结构可以描述为(4,4)-连接的拓扑,拓扑符号为(44·62)。配合物8是一价铜离子和L3配体构成(6,3)-连接的二维层状结构。3、利用3,5-二(吡啶-4-甲氧基)苯甲酸(HL1),3,4-二(吡啶-4-甲氧基)苯甲酸(HL2),共配体1,4-bdc和d10过渡金属在水热条件下,得到两个配合物:[Zn2(L1)2(1,4-bdc)] (9), [Zn3(HL2)(1,4-bdc)3] (10)。配合物9是由1,4-bdc配体柱撑Zn-L1二维层,形成具有四重互穿的(3,4)-连接网络结构。配合物10中,L2配体的羧基被质子化,形成5-连接二维层状结构。其拓扑符号为(33·44·53)。更多还原

【Abstract】 Coordination polymer has attracted much more interests as its flexible tailoring, various topologies and potential applications in gas storage, catalysts and magnetism. According to the principle of molecular engineering, it is possible to realize rational design and synthesis of novel multifunctional materials by selecting certain metal ions and suitable organic ligands.In this dissertation, we have focused the influence of the metal ions, organic ligands and coligands on secondary building units and compound structures under hydrothermal condition. The synthetic conditions, topology of 10 compounds have been studied. Several factors influencing the final structures, such as the coordination modes of metal ions, the properties of organic ligands, pH value of reaction conditions were discussed. Furthermore, fluorescent property and the thermal stabilities have also been studied. The main contents are summarized as below:1. Three novel 3D (3,8)-connected compounds, [Cd2(L1)2(1,3-bdc)] (1), [Cd2(L2)2(1,4-bdc)]·3H2O (2), [Cd3(L3)2(1,3-bdc)2] (3), have been synthesized based on the combination of flexible HL1 (HL2 or HL3) ligand and rigid benzenedicarboxylate ligand with Cd2-based (or Cd3-based) SBUs under hydrothermal conditions. Compounds 1 and 3 present novel (3,8)-connected nets with unprecedented (42·6)2(44·622·82) and (42·5)2(44·56·610·75·82·9) topology notations; compound 2 is a tfz-d net with (43)2(46·618·84) topology symbol.2. Five new compounds, [Cd(L3)2]·H2O (4), [Zn(L3)2] (5), [Co(L3)2] (6), [Ni(L3)2] (7) and [Cu2(L3)2]·3H2O (8), have been hydrothermally synthesized on the basis of 3,5-bis(pyridin-3-ylmethoxy)benzoic acid (HL3) and d10 transition metal ions. Compound 4 is a binodal (3,4)-connected net with (63)(66) topology. Compounds 5-7 are isostructural, thus, only the structure of 5 is representatively described in detail here. In the crystal structure, the adjacent helical chains are linked by L3 ligands to generate a 2D rhombic structure involving 44-membered rings. With in the layer, all Zn-L3 helical chains display the same chirality, while those in adjacent layers display opposite chirality. Therefore, the overall structure of 5 is a racemic structure. The topology of 5 can be described by the uninodal (4,4)-connected net with (44·62) Schl?fli symbol. The structure of 8 is a 2D binodal (6,3)-connected net constructed by CuI and L3 ligand. 3. Two new compounds, [Zn2(L1)2(1,4-bdc)] (9), [Zn3(L2)(1,4-bdc)3] (10), have been hydrothermally synthesized on the basis of 3,5-bis(pyridin-4-ylmethoxy)benzoic acid (HL1) (or 3,4-bis(pyridin-4-ylmethoxy)benzoic acid (HL2), 1,4-benzenedicarboxylic acid and d10 transition metal ions. Compound 9 displays a 3D 4-fold interpenetrating (3,4)-connected net with (4·82)(4·85) topology. Compound 10 with the carboxybenzyloxyl group undeprotonation of L2 ligand, is a 2D 5-connected network with the (33·44·53) topology.更多还原