过渡金属—柔性芳香多羧酸配位聚合物的合成、结构及性质研究
发布时间：2018-09-06 17:03
【摘要】：配位聚合物在构筑过程中因受有机配体、中心金属离子和反应条件(如温度、pH、溶剂等)等因素的影响,预测其拓扑结构具有难度。研究这些因素影响的规律对配位聚合物的设计与合成具有指导意义。柔性多羧酸配体根据不同反应条件可呈现不同的构象从而构筑出结构丰富多样的配位聚合物,因而吸引着众多研究人员的兴趣。本论文基于四种柔性芳香多羧酸配体与过渡金属在水热条件下自组装制备得到8个配位聚合物,主要研究内容如下:一、设计合成了四种含醚键(C-O-C)柔性多羧酸配体和一种含氮杂环辅配体:4,4'-(1,4-苯二氧基)双苯甲酸(H2L1)、4,4'-(1,3-苯二氧基)双苯甲酸(H2L2)、1,3-二[3,5-(二羧基)苯氧基]-2-羟基丙烷(H_4L_3)、均三甲苯基-1,3,5-三亚甲基氧代-间三苯二甲酸(H6L4)和1,1′-(1,4-丁基)二苯并咪唑(bbbm)。配体H2L1与H2L2含Ar-O-Ar单元,属于既含刚性又具有柔性的半柔性多羧酸配体。配体H_4L_3与H6L4均为基于间苯二酸为构筑单元的多羧酸柔性配体。五种配体均经红外(IR)、核磁共振氢谱(1H-NMR)验证。二、基于以上柔性多羧酸配体,通过改变中心金属离子、溶剂、pH值等条件合成了8个新颖的配位聚合物:[Mn(L1)(H_2O)2]n(1)、[Cd(L1)(H_2O)2]n(2)、[Zn(L2)(bbbm)0.5]n(3)(bbbm=1,1′-(1,4-butanediyl)bisbenzimidazole)、[Co(L2)(bbbm)]n(4)、[Cd(L2)(bbbm)]n(5)、[Cu2(L3)(H_2O)3]n(6)、[Cd2(L3)(H_2O)6]n(7)及[Cd2(L4)(H_2O)4]n(8)。通过元素分析、红外光谱(IR)及X-射线粉末衍射(PXRD)分别对所有配合物进行表征;利用单晶X-射线衍射对配合物晶体结构进行分析。同时,还研究了所有配合物的热稳定性、固体荧光性质和部分配合物的磁学性质。三、配合物1和2属于同构类型,呈现三维dia网络拓扑结构,顶点符号为[6(2).6(2).6(2).6(2).6(2).6(2)]。配合物3、4和5是由配体H2L2构筑的二维配位聚合物,其中配合物4与5为同构类型,他们呈现聚轮烷和聚索烃共存的二重穿插2D网络结构,Schl?fli拓扑符号为{63}。而配合物3在结构上与配合物4和5存在较大差异,其拓扑类型为sql,点符号为(44.62)。配合物3与4/5结构上的差异表明金属中心离子对配位聚合物的框架结构存在明显的影响。配合物4和5在荧光和磁性方面存在较大的差异,这也表明金属中心离子对配位聚合物的性能存在显著的影响。四、配合物6是基于H_4L_3构筑的三维拓扑类型,Schl?fli符号为{42.64}{42.84}。该配合物通过有机配体阴离子将kagomé型二维网络联接成三维网络结构,结构中含有两种大小的孔径,具有潜在的吸附性能。磁学研究表明,该配合物内部主要呈现反铁磁相互作用。配合物7和8是分别基于配体H_4L_3和H6L4的二维配位聚合物,它们具有相同的点符号(63)。配合物7呈现ABCABC堆积,而配合物8则以ABAB形式堆积。两者都有较好的热稳定性及荧光性能,可用作功能性发光材料。
[Abstract]:It is difficult to predict the topological structure of coordination polymers due to the influence of organic ligands, central metal ions and reaction conditions (such as temperature, pH, solvent, etc.). The study of the influence of these factors on the design and synthesis of coordination polymers is of great significance. Flexible polycarboxylic acid ligands can present different conformation according to different reaction conditions, and thus construct coordination polymers with rich and diverse structures, which has attracted the interest of many researchers. In this thesis, eight coordination polymers were prepared by self-assembly of four flexible aromatic polycarboxylic acid ligands and transition metals under hydrothermal conditions. The main contents are as follows: 1. Four kinds of flexible polycarboxylic acid ligands containing ether bond (C-O-C) and a nitrogen-containing heterocyclic coligand, 1: 4- (1o 4- phenyldioxy) dibenzoic acid (H2L1) 4- (1, 3-phenyldioxy) dichlorobenzoic acid (H2L2), 13-bis (dicarboxylic) phenoxy] -2-hydroxypropane (H_4L_3), are designed and synthesized. Trimethylenedioxylic acid (H6L4) and 1-dibenzimidazole (bbbm). Ligands H2L1 and H2L2 contain Ar-O-Ar units and belong to semi-flexible polycarboxylic acid ligands with rigidity and flexibility. Both ligands H_4L_3 and H6L4 are polycarboxylic acid flexible ligands based on isophthalic acid. The five ligands were confirmed by (IR), NMR hydrogen NMR (1H-NMR). 浜，
本文编号：2226986
[Abstract]:It is difficult to predict the topological structure of coordination polymers due to the influence of organic ligands, central metal ions and reaction conditions (such as temperature, pH, solvent, etc.). The study of the influence of these factors on the design and synthesis of coordination polymers is of great significance. Flexible polycarboxylic acid ligands can present different conformation according to different reaction conditions, and thus construct coordination polymers with rich and diverse structures, which has attracted the interest of many researchers. In this thesis, eight coordination polymers were prepared by self-assembly of four flexible aromatic polycarboxylic acid ligands and transition metals under hydrothermal conditions. The main contents are as follows: 1. Four kinds of flexible polycarboxylic acid ligands containing ether bond (C-O-C) and a nitrogen-containing heterocyclic coligand, 1: 4- (1o 4- phenyldioxy) dibenzoic acid (H2L1) 4- (1, 3-phenyldioxy) dichlorobenzoic acid (H2L2), 13-bis (dicarboxylic) phenoxy] -2-hydroxypropane (H_4L_3), are designed and synthesized. Trimethylenedioxylic acid (H6L4) and 1-dibenzimidazole (bbbm). Ligands H2L1 and H2L2 contain Ar-O-Ar units and belong to semi-flexible polycarboxylic acid ligands with rigidity and flexibility. Both ligands H_4L_3 and H6L4 are polycarboxylic acid flexible ligands based on isophthalic acid. The five ligands were confirmed by (IR), NMR hydrogen NMR (1H-NMR). 浜，
本文编号：2226986
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