基于萘乙酸及含氮杂环分子配体功能配合物的合成、晶体结构和性能
发布时间：2019-05-09 19:20
【摘要】：金属-有机配合物在光学、磁性、催化、气体吸附和分离等方面具有优良的性能,受到人们广泛关注,已成为当今配位化学的研究热点。有机配体的精心选择和设计在晶体工程及超分子的构建中十分重要。有机羧酸和含氮类配体的配位方式多样,配位能力强,一直是化学家的研究热点。利用芳香羧酸a-萘乙酸(α-HNAA)或p-萘乙酸(p-HNAA)分别与2-乙基咪唑(2-Etlm)和2-丙基咪唑(2-Prlm)、苯并咪唑(bim)、5,6-二甲基苯并咪唑(DMB)、1,4-二(苯并咪唑-1-基)丁烷(bbbm)、1,4-二(5,6-二甲基苯并咪唑-1-基)丁烷(bbdmbm)、1,4-二(苯并咪唑-1-甲基)苯(bbix)、1,4-二(2-甲基苯并咪唑-1-基)丁烷(bbmb)与过渡金属离子反应合成了25个结构新的配位化合物：[Mn(a-NA A)2(H2O)2] (1)、[Cu(α-NAA)2] (2)、[Zn(α-NAA)2(H2O)2] (3)、[Cu4(α-NAA)8(CH3CN) 2] (4)、[Cu(2-Etlm)2(α-NAA)2] (5)、[Ni(2-Etlm)2(α-NAA)2] (6)、[Cd(2-Etlm)2(α-NAA) 2] (7)、[Ni(2-Prlm)2(α-NAA)2] (8)、[Co(2-Prlm)2(α-NAA)2] (9)、[Cd(2-Prlm)2(α-NAA) 2] (10)、[Cu(bim)2(α-NAA)2-H2O] (11)、[Cu2(bim)4(α-NAA)4-2H2O] (12)、[Mn(bim)2(α-NAA)2-H2O] (13)、[Ni(bim)2(α-NAA)2-H2O] (14)、[Co(bim)2(α-NAA)2-H2O] (15)、[C u(DMB)2(α-NAA)2]2 (16)、[Co(DMB)2(α-NAA)2] (17)、[Ni(DMB)2(α-NAA)] (18)、[Z n(DMB)2(α-NAA)Cl] (19)、[Cd(DMB)2(α-NAA)2] (20)、[Co(bbbm)(α-NAA)2] (21)、[C o(bbdmbm)(α-NAA)2] (22)、[Ni(bbmb)(α-NAA)2] (23)、[Ni(bbix)(β-NAA)2]及[Ni (bbix)(β-NAA)2] (25)。通过元素分析、红外光谱、粉末衍射等对配合物进行了初步结构表征,进一步采用单晶X-射线衍射测试了晶体结构。采用热重-差热分析、荧光光谱、循环伏安法、变温磁化率等测试研究了配合物的热稳定性、荧光、电化学、磁性质。配合物2是一维链状结构,它的铜离子被五个来自五个萘乙酸根的氧原子配位形成了一个略微扭曲的四方锥几何构型。磁性质研究表明：相邻的铜离子间存在强的反铁磁耦合作用。配合物11的固体样品在加热到50℃后,由黄色变为草绿色,再降至室温后,又恢复为黄色,表明11具有热致变色的性质。分析了热致变色的产生原因。配聚物16和17对有机染料刚果红具有很好的催化降解活性,降解符合准一级反应动力学。配合物16在80分钟后的降解率达到了96.9%,可作为潜在的催化材料。配合物9、10、13、15、21、23和25表现出良好的荧光性能,在荧光方面具有潜在的应用前景。这些配合物均呈现出较好的热稳定性。
[Abstract]:Metal-organic complexes have excellent properties in optics, magnetism, catalysis, gas adsorption and separation, and have been paid more and more attention, and have become the research focus of coordination chemistry. The careful selection and design of organic ligands are very important in crystal engineering and supramolecular construction. Organic carboxylic acids and nitrogen-containing ligands have a variety of coordination modes and strong coordination ability, which has been a hot research topic for chemists. Aromatic carboxylic acid a-Naphthylacetic acid (伪-HNAA) or p-Naphthylacetic acid (p-HNAA) were used with 2-ethylimidazole (2-Etlm) and 2-propylimidazole (2-Prlm), benzimidazole (bim), 5, 6-dimethyl benzimidazole (DMB), respectively. 1, 4-bis (benzimidazole-1-yl) butane (bbbm), 1, 4-bis (5, 6-dimethyl benzimidazole-1-yl) butane (bbdmbm), 1, 4-bis (benzimidazole-1-methyl) benzene (bbix), 1, 25 new coordination compounds were synthesized by the reaction of 4-bis (2-methylbenzimidazole-1-yl) butane (bbmb) with transition metal ions: [Mn (a-NA A) 2 (H2O) 2] (1), [Cu (伪-NAA) 2] (2), [Zn (伪-NAA) 2 (H2O) 2] (3), [Cu4 (伪-NAA) 8 (CH3CN) 2] (4), [Cu (2-Etlm) 2 (伪-NAA) 2] (5), [Ni (2-Etlm) 2 (伪-NAA) 2] (6), [Cd (2-Etlm) 2 (伪-NAA) 2] (7), [Ni (2-Prlm) 2 (伪-NAA) 2] (8), [Co (2-Prlm) 2 (伪-NAA) 2] (9), [Cd (2-Prlm) 2 (伪-NAA) 2] (10), [Cu (bim) 2 (伪-NAA) 2-H2O] (11), [Cu2 (bim) 4 (伪-NAA) 4-2H2O] (12), [Mn (bim) 2 (伪-NAA) 2-H2O] (13), [Ni (bim) 2 (伪-NAA) 2-H2O] (14), [Co (bim) 2 (伪-NAA) 2-H2O] (15), [C u (DMB) 2 (伪-NAA) 2] 2 (16), [Co (DMB) 2 (伪-NAA) 2] (17), [Ni (DMB) 2 (伪-NAA)] (18), [Z n (DMB) 2 (伪-NAA) Cl] (19), [Cd (DMB) 2 (伪-NAA) 2] (20), [Co (bbbm) (伪-NAA) 2] (21), [Co (bbdmbm) (伪-NAA) 2] (22), [Ni (bbmb) (伪-NAA) 2] (23), [Ni (bbix) (尾-NAA) 2] and [Ni (bbix) (尾-NAA) 2] (25). The structure of the complex was characterized by elemental analysis, infrared spectroscopy and powder diffraction, and the crystal structure was further measured by single crystal X-ray diffraction. The thermal stability, fluorescence, electrochemical and magnetic properties of the complexes were studied by thermogravimetric-differential thermal analysis, fluorescence spectroscopy, cyclic Voltammetric method and variable temperature magnetic susceptibility. Complex 2 is a one-dimensional chain structure, and its copper ions are coordinated by five oxygen atoms from five naphthoacetic acid to form a slightly twisted tetrahedral cone geometry. The study of magnetic properties shows that there is strong antiferromagnetic coupling between adjacent copper ions. The solid sample of complex 11 changed from yellow to grass green after heating to 50 鈩，
本文编号：2473021
[Abstract]:Metal-organic complexes have excellent properties in optics, magnetism, catalysis, gas adsorption and separation, and have been paid more and more attention, and have become the research focus of coordination chemistry. The careful selection and design of organic ligands are very important in crystal engineering and supramolecular construction. Organic carboxylic acids and nitrogen-containing ligands have a variety of coordination modes and strong coordination ability, which has been a hot research topic for chemists. Aromatic carboxylic acid a-Naphthylacetic acid (伪-HNAA) or p-Naphthylacetic acid (p-HNAA) were used with 2-ethylimidazole (2-Etlm) and 2-propylimidazole (2-Prlm), benzimidazole (bim), 5, 6-dimethyl benzimidazole (DMB), respectively. 1, 4-bis (benzimidazole-1-yl) butane (bbbm), 1, 4-bis (5, 6-dimethyl benzimidazole-1-yl) butane (bbdmbm), 1, 4-bis (benzimidazole-1-methyl) benzene (bbix), 1, 25 new coordination compounds were synthesized by the reaction of 4-bis (2-methylbenzimidazole-1-yl) butane (bbmb) with transition metal ions: [Mn (a-NA A) 2 (H2O) 2] (1), [Cu (伪-NAA) 2] (2), [Zn (伪-NAA) 2 (H2O) 2] (3), [Cu4 (伪-NAA) 8 (CH3CN) 2] (4), [Cu (2-Etlm) 2 (伪-NAA) 2] (5), [Ni (2-Etlm) 2 (伪-NAA) 2] (6), [Cd (2-Etlm) 2 (伪-NAA) 2] (7), [Ni (2-Prlm) 2 (伪-NAA) 2] (8), [Co (2-Prlm) 2 (伪-NAA) 2] (9), [Cd (2-Prlm) 2 (伪-NAA) 2] (10), [Cu (bim) 2 (伪-NAA) 2-H2O] (11), [Cu2 (bim) 4 (伪-NAA) 4-2H2O] (12), [Mn (bim) 2 (伪-NAA) 2-H2O] (13), [Ni (bim) 2 (伪-NAA) 2-H2O] (14), [Co (bim) 2 (伪-NAA) 2-H2O] (15), [C u (DMB) 2 (伪-NAA) 2] 2 (16), [Co (DMB) 2 (伪-NAA) 2] (17), [Ni (DMB) 2 (伪-NAA)] (18), [Z n (DMB) 2 (伪-NAA) Cl] (19), [Cd (DMB) 2 (伪-NAA) 2] (20), [Co (bbbm) (伪-NAA) 2] (21), [Co (bbdmbm) (伪-NAA) 2] (22), [Ni (bbmb) (伪-NAA) 2] (23), [Ni (bbix) (尾-NAA) 2] and [Ni (bbix) (尾-NAA) 2] (25). The structure of the complex was characterized by elemental analysis, infrared spectroscopy and powder diffraction, and the crystal structure was further measured by single crystal X-ray diffraction. The thermal stability, fluorescence, electrochemical and magnetic properties of the complexes were studied by thermogravimetric-differential thermal analysis, fluorescence spectroscopy, cyclic Voltammetric method and variable temperature magnetic susceptibility. Complex 2 is a one-dimensional chain structure, and its copper ions are coordinated by five oxygen atoms from five naphthoacetic acid to form a slightly twisted tetrahedral cone geometry. The study of magnetic properties shows that there is strong antiferromagnetic coupling between adjacent copper ions. The solid sample of complex 11 changed from yellow to grass green after heating to 50 鈩，
本文编号：2473021
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