几种多羧酸配合物的合成及其结构和性质研究
发布时间:2018-10-12 12:30
【摘要】:金属有机框架(MOFs)化合物因其新颖的结构和多样化的功能而受到了越来越广泛的关注,成为当前无机化学、物理化学、材料化学等学科的前沿性交叉热点之一。多羧酸类有机桥连配体由于羧酸根的强配位能力及配位方式的灵活多样性,因此成为构筑多功能金属-有机骨架材料的常用有机配体。在本论文中,我们分别以5-氨基间苯二甲酸、5-羟基间苯二甲酸、间氨基苯甲酸和对羟基苯乙酸为原料合成了五种芳香多羧酸配体或配体的衍生物。以所得配体或配体的衍生物与金属离子反应,得到11个配合物。通过红外、粉末X-射线衍射、单晶X-射线衍射、核磁等手段对所得产物进行了表征,并对配合物的结构和性质进行了研究。采用戊酰胺基-3,5-苯二甲酸二甲酯((Me)2L1)为配体,与Zn离子进行配位反应,合成配合物[Zn(L1)]n(1);以三氟乙酰胺基-3,5-苯二甲酸二甲酯((Me)2L2)为配体,与Cd和Co离子反应,得到2个配合物:{[Cd(L2)(H2O)]·2H2O}n (2)和{[Co(L2)2·(H2O)2]·2H2O}n (3)。研究了配合物 1-3 的结构和配体的配位方式。采用5- (2-羟基乙氧基)间苯二甲酸二甲酯((Me)2L3)为配体,4, 4-联吡啶为助配剂,与金属Cd和Cu离子反应,得到两个配合物:{[Cd2(L3)2(bpy)(H20)4].4H20}n (4)和[Cu2(L3)2(bpy)(H2O)4]n (5),研究发现 4和5在一定金属离子浓度条件下可以进行彼此之间的相互转化。以5- (2-羟基乙氧基)间苯二甲酸(H2L3)为配体,与Sm、Eu、Tb离子反应,得到三个结构相同的配合物:{SmL3(HL3)(H2O)2}n (6)、{EuL3(HL3)(H2O)2}n (7)和{TbL3(HL3)(H2O2}n (8)。研究了配合物 6-8 的热稳定性和光致发光特性。采用3-(3-羟基)-4-羟基偶氮苯乙酸(H2L4)为配体,与金属Co和Mn离子进行反应,得到两个结构一致的配合物分子{[Co(L4)2(H2O)4]·2H2O} (9)和{[Mn(L4)2(H2O)4]-2H2O} (10);以 3-(3-羟基)-4-烯丙氧基偶氮苯乙酸(H2L5)为配体,与Zn离子反应,得到一个具有单一手性的螺旋结构配合物[Zn(L5)(H2O)2]n (11),讨论了配合物11的紫外吸收特性。对配位化合物结构的研究有助于我们推测其性能,而对配合物性质的研究将为配合物的实际应用提供更加广阔的前景。
[Abstract]:Organometallic frame (MOFs) compounds have attracted more and more attention due to their novel structure and diverse functions, and have become one of the leading intersecting hotspots in inorganic chemistry, physical chemistry, material chemistry and so on. Polycarboxylic acid organic bridging ligands have become common organic ligands for the construction of multifunctional metal-organic skeleton materials due to their strong coordination ability and flexible variety of coordination modes. In this thesis, five aromatic polycarboxylic acid ligands or their derivatives were synthesized from 5-amino-isophthalic acid, 5-hydroxyisophthalic acid, m-aminobenzoic acid and p-hydroxyphenylacetic acid, respectively. Eleven complexes were obtained by the reaction of the ligand or ligand derivatives with metal ions. The products were characterized by IR, powder X ray diffraction, single crystal X ray diffraction and NMR. The structure and properties of the complexes were also studied. The complexes [Zn (L1)] n (1) were synthesized by the ligand of dimethyl pentanediformate (Me) 2L1) and reacted with Cd and Co ions. Two complexes {[Cd (L2) (H2O)] 2H2O} n (2) and {[Co (L2) 2 (2) 2] 2H2O} n (3) were synthesized. The structure of complex 1-3 and the coordination mode of ligand were studied. Using 5- (2-hydroxy-ethoxy) dimethyl isophthalate (Me) 2L3) as ligand and 4,4-bipyridine as coagent, the reaction was carried out with metal Cd and Cu ions. Two complexes {[Cd2 (L3) 2 (bpy) (H20) 4]. 4H20} n (4) and [Cu2 (L3) 2 (bpy) (H2O) 4] n (5) were obtained. Using 5- (2-hydroxyethoxy) isophthalic acid (H2L3) as ligand, three complexes with the same structure were obtained by reaction with Sm,Eu,Tb ion: {SmL3 (HL3) (H2O) 2} n (6), {EuL3 (HL3) (H2O) 2} n (7) and {TbL3 (HL3) (H2O2} n (8). The thermal stability and photoluminescence properties of complex 6-8 were studied. Using 3- (3-hydroxy-4-hydroxyphenylacetic acid) (H2L4) as ligand, two complexes {[Co (L _ 4) _ 2 (H _ 2O) _ 4] 2H2O} (9) and {[Mn (L _ 4) _ 2 (H _ 2O) _ 4] -2H2O} (10) were synthesized by reaction with metal Co and Mn ions. A single chiral helical complex [Zn (L _ 5) (H _ 2O) _ 2] n (11) was obtained. The UV absorption characteristics of the complex 11 were discussed. The study of the structure of the coordination compounds will help us to speculate on their properties, while the study of the properties of the complexes will provide a broader prospect for the practical application of the complexes.
【学位授予单位】:山东科技大学
【学位级别】:硕士
【学位授予年份】:2017
【分类号】:O641.4
本文编号:2266121
[Abstract]:Organometallic frame (MOFs) compounds have attracted more and more attention due to their novel structure and diverse functions, and have become one of the leading intersecting hotspots in inorganic chemistry, physical chemistry, material chemistry and so on. Polycarboxylic acid organic bridging ligands have become common organic ligands for the construction of multifunctional metal-organic skeleton materials due to their strong coordination ability and flexible variety of coordination modes. In this thesis, five aromatic polycarboxylic acid ligands or their derivatives were synthesized from 5-amino-isophthalic acid, 5-hydroxyisophthalic acid, m-aminobenzoic acid and p-hydroxyphenylacetic acid, respectively. Eleven complexes were obtained by the reaction of the ligand or ligand derivatives with metal ions. The products were characterized by IR, powder X ray diffraction, single crystal X ray diffraction and NMR. The structure and properties of the complexes were also studied. The complexes [Zn (L1)] n (1) were synthesized by the ligand of dimethyl pentanediformate (Me) 2L1) and reacted with Cd and Co ions. Two complexes {[Cd (L2) (H2O)] 2H2O} n (2) and {[Co (L2) 2 (2) 2] 2H2O} n (3) were synthesized. The structure of complex 1-3 and the coordination mode of ligand were studied. Using 5- (2-hydroxy-ethoxy) dimethyl isophthalate (Me) 2L3) as ligand and 4,4-bipyridine as coagent, the reaction was carried out with metal Cd and Cu ions. Two complexes {[Cd2 (L3) 2 (bpy) (H20) 4]. 4H20} n (4) and [Cu2 (L3) 2 (bpy) (H2O) 4] n (5) were obtained. Using 5- (2-hydroxyethoxy) isophthalic acid (H2L3) as ligand, three complexes with the same structure were obtained by reaction with Sm,Eu,Tb ion: {SmL3 (HL3) (H2O) 2} n (6), {EuL3 (HL3) (H2O) 2} n (7) and {TbL3 (HL3) (H2O2} n (8). The thermal stability and photoluminescence properties of complex 6-8 were studied. Using 3- (3-hydroxy-4-hydroxyphenylacetic acid) (H2L4) as ligand, two complexes {[Co (L _ 4) _ 2 (H _ 2O) _ 4] 2H2O} (9) and {[Mn (L _ 4) _ 2 (H _ 2O) _ 4] -2H2O} (10) were synthesized by reaction with metal Co and Mn ions. A single chiral helical complex [Zn (L _ 5) (H _ 2O) _ 2] n (11) was obtained. The UV absorption characteristics of the complex 11 were discussed. The study of the structure of the coordination compounds will help us to speculate on their properties, while the study of the properties of the complexes will provide a broader prospect for the practical application of the complexes.
【学位授予单位】:山东科技大学
【学位级别】:硕士
【学位授予年份】:2017
【分类号】:O641.4
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