發(fā)布時間：2018-10-12 12:30

【摘要】：金屬有機框架(MOFs)化合物因其新穎的結(jié)構(gòu)和多樣化的功能而受到了越來越廣泛的關(guān)注,成為當前無機化學、物理化學、材料化學等學科的前沿性交叉熱點之一。多羧酸類有機橋連配體由于羧酸根的強配位能力及配位方式的靈活多樣性,因此成為構(gòu)筑多功能金屬-有機骨架材料的常用有機配體。在本論文中,我們分別以5-氨基間苯二甲酸、5-羥基間苯二甲酸、間氨基苯甲酸和對羥基苯乙酸為原料合成了五種芳香多羧酸配體或配體的衍生物。以所得配體或配體的衍生物與金屬離子反應,得到11個配合物。通過紅外、粉末X-射線衍射、單晶X-射線衍射、核磁等手段對所得產(chǎn)物進行了表征,并對配合物的結(jié)構(gòu)和性質(zhì)進行了研究。采用戊酰胺基-3,5-苯二甲酸二甲酯((Me)2L1)為配體,與Zn離子進行配位反應,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)為配體,與Cd和Co離子反應,得到2個配合物:{[Cd(L2)(H2O)]·2H2O}n (2)和{[Co(L2)2·(H2O)2]·2H2O}n (3)。研究了配合物 1-3 的結(jié)構(gòu)和配體的配位方式。采用5- (2-羥基乙氧基)間苯二甲酸二甲酯((Me)2L3)為配體,4, 4-聯(lián)吡啶為助配劑,與金屬Cd和Cu離子反應,得到兩個配合物:{[Cd2(L3)2(bpy)(H20)4].4H20}n (4)和[Cu2(L3)2(bpy)(H2O)4]n (5),研究發(fā)現(xiàn) 4和5在一定金屬離子濃度條件下可以進行彼此之間的相互轉(zhuǎn)化。以5- (2-羥基乙氧基)間苯二甲酸(H2L3)為配體,與Sm、Eu、Tb離子反應,得到三個結(jié)構(gòu)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 的熱穩(wěn)定性和光致發(fā)光特性。采用3-(3-羥基)-4-羥基偶氮苯乙酸(H2L4)為配體,與金屬Co和Mn離子進行反應,得到兩個結(jié)構(gòu)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-羥基)-4-烯丙氧基偶氮苯乙酸(H2L5)為配體,與Zn離子反應,得到一個具有單一手性的螺旋結(jié)構(gòu)配合物[Zn(L5)(H2O)2]n (11),討論了配合物11的紫外吸收特性。對配位化合物結(jié)構(gòu)的研究有助于我們推測其性能,而對配合物性質(zhì)的研究將為配合物的實際應用提供更加廣闊的前景。
[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.
【學位授予單位】：山東科技大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O641.4

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本文編號：2266121