芳香羧酸类配合物的组装、晶体结构与性质研究

【作者】 刘念丽；

【导师】 田来进；

【作者基本信息】 曲阜师范大学 ， 无机化学， 2010， 硕士

【摘要】 配位聚合物因具有新奇多样的拓扑结构和作为功能材料的潜在应用价值而成为当今配位化学研究的热点之一。在构造配位聚合物时,金属离子的选择是有限的,配体的选择却是无限的。通过选择合适的桥联配体可以构筑新奇的配位聚合物。有机芳香羧酸配体作为含氧配体的重要家族之一就是常用的配体。芳香羧酸配体有多种配位方式,可以与多种金属中心配位形成多维结构。配位羧酸聚合物已被广泛应用于催化、材料、医药等很多领域。本论文选择以3,4,5,6-四氟邻苯二甲酸、9,10-二氢化蒽-9,10-内型-α,β-丁二酸、4,4’-异丙基双(2,6-苯氧乙酸)、5-甲基-2-羟基-1,5-间苯二甲酸为第一配体,以咪唑、2-甲基咪唑、2-乙基咪唑、2,2’-联吡啶、4,4’-联吡啶,1,10-啡咯啉、吡唑为辅助配体,合成了20个未见报道结构新颖的羧酸类金属配合物,分别用红外、元素分析和X-射线单晶衍射对其进行了表征,解析了18个配合物的晶体结构,研究了部分代表性配合物的荧光性质和电化学性质。主要结果如下：1.以四氟邻苯二甲酸(tfpa)为第一配体,以咪唑(im),1,10-菲咯啉(1,10-phen)、2-甲基咪唑(Meim)、2-乙基咪唑(Etim)、吡唑(pyra)、2,2’-联吡啶(2,2-bipy)、4.4’-联吡啶(4,4’-bipy)为第二配体,用溶液挥发法和扩散法合成了11个过渡金属配合物[Cu(tfpa)2(o-phen)2](1A); [Co(tfpa)(o-phen)2](2A);[Co(tfpa)(2,2’-bipy)2](3A);[Zn(tfpa)(o-phen)2] (NO3)](4A);[Zn2(tfpa)2(2,2’-bipy)2](5A);[Zn2(tfpa)2(2-EI)4](6A);[Zn(tfpa)(im)2](7A);[Zn(tfpa)(2-meim)2](8A);[Zn(tfpa)(pyra)2](9A);(4,4’-bipy)2]n(10A);[Mn (tfpa)(1,10-phen)2](11A)。用X-射线单晶衍射对以上晶体进行了表征,解析出了它们的晶体结构,1A、6A、8A通过分子间作用力相互吸引形成畸变的四面体结构；2A通过分子间氢键形成一维链状结构；3A、7A、10A、11A通过分子间氢键形成二维的平面结构；4A、5A通过分子内氢键形成一个齿轮状结构；9A通过分子间作用力形成一维链状结构。测定了代表性配合物1 A的电化学性质,结果表明配合物中的金属离子比自由的金属离子稳定。2.以9,10-二氢化蒽-9,10-内型-α,β-丁二酸(dasa)为主配体,2-乙基咪唑(Etim)、1,10-啡咯啉(1,10-phen)作为辅助配体,用水热合成法合成了5个过渡金属配合物,[Cd (dasa) (1,10-phen)2](1B)、[Zn(dasa) (1,10-phen)2]n(2B)、{Ni2 [dasa]2 (H2O)2}(3B)、{Ni [dasa] (1,10-phen)2} (4B)、[Zn2(dasa)2 (2-ethylimi)2]n(5B)。对以上5个晶体的结构进行了解析,1B通过分子内氢键形成一维链状结构,2B、4B通过分子间作用力形成畸变的八面体,3B通过分子间作用力形成平面四边形,5B通过分子间氢键形成二维结构。测定了代表性配合物的热稳定性。结果表明对9,10-二氢化蒽-9,10-内型-α,β-丁二酸这样难溶性的配体,反应温度、体系的PH值,反应时间,降温速度对晶体的形成都有很大的影响。3、以4,4’-异丙基双(2,6-苯氧乙酸)(bdta)为配体,与硝酸锌和硝酸镉反应,合成了1个晶体1C和粉末2 C,并解析了配体与锌离子形成的配位聚合物(1C)的结构。同时用红外表征了这两种化合物,得出1C通过分子间作用力形成了一维的螺旋状结构。并研究了代表性配合物1C的热稳定性质。4、以5-甲基-2-羟基-1,5-间苯二甲酸为配体,与硝酸镉和硝酸锌反应,合成了1个晶体化合物1D和粉末2D,并解析出1D的晶体结构为三维的笼状结构。同时测定研究了1D的荧光性质。更多还原

【Abstract】 Because the acid complexes have many kinds of coordinate structures and potential application of functional materials, now they become one of coordination chemistry research hot spots. In constructing coordination polymers, the metal ions choice is limited; the choice of ligand is unlimited. By choosing the appropriate bridging ligand can build novel coordination polymers. Organic aromatic carboxylic acid ligands as the oxygen-containing ligands are one of the important families of ligands. Aromatic carboxylic acid ligands have a variety of coordination, so it can be a variety of metal center coordination with the formation of multi-dimensional structure. Coordination carboxylic acid polymers have been widely used in catalysis, materials, medicine and many other fields.The paper take 3,4,5,6-tetrafluorophthalic acid,9,10-anthracene dihydride-9,10-fo rmers-α,β-succinic acid,4,4’-isopropyldouble(2,6-phenoxyacetic acid),2-hydroxy-5-methyliso phthalic acid as the first ligands to synthesize 20 new coordinatiaon compounds having n ot been reported with imidazole2-methy-imidazole,2-ethyl-imidazole,2,2’-bipyridine,4,4’-bipy ridine,1,10-phenanthroline,pyrazole as the second ligands.These complexes were characteriz ed by FT-IR,elemental analysis and X-ray crystallography and 18 crystal structure of comp lexes were analysised.Electrochemical properties and fluorescence properties of several co ordination compounds were studied. Main results are as follows:1.3,4,5,6-tetrafluorophthalic acid was selected as the first ligand to synthesize 11 new coordination compounds through solution reaction with imidazole,l,10-phenanthroli ne,2-methyimidazole,2-ehyl-imidazole,pyrazole,2,2’-bipyridine,4,4’-bipyridine as the second 1 igands. [Cu(tfpa)2(o-phen)2](1 A)、[Co (tfpa)(o-phen)2] (2 A)、[Co (tfpa)(2,2’-bipy)2] (3 A)、[Zn (tfpa)(o-phen)2] (NO3)] (4 A)、[Zn2 (tfpa) 2(2,2’-bipy)2](5 A)、[Zn2 (tfpa) 2(2-EI) 4](6 A)、[Zn (tfpa) (im)2](7 A)、[Zn (tfpa) (2-meim)2](8 A)、[Zn (tfpa) (pyra)2](9 A)、(4, 4’-bipy)2]n(10 A)、[Mn (tfpa) (1,10-phen)2](11 A)。The above crystals were characterized parsing out their crystal structure with the X-ray diffraction.1A,6A,8A form distorted te trahedral structure through mutual attraction forces.2A is one-dimensional structure linked by H2O molecular; 3A,7A,10A,11A form two-dimensional planar structure through th e intermolecular hydrogen bonding; 4A,5 A form a gear-like structure through intramolec ular hydrogen bonds; 9A form one-dimensional chain structure through intermolecular for ces. Representation of the 1 A was determined by the electrochemical properties which s hows that metal ions which exit in the compounds are more stable than free ions.2.9,10-dihydro anthracene-9,10-endo-a,B-succinic acid was selected as the first ligand to synthesize 5 new coordination compounds through hydrothermal synthesis with 2-ehyl -imidazole,1,10-phenanthroline as the second ligands.[Cd (dasa) (1,10-phen) 2](1B);[Zn(das a)(1,10-phen)2]n(2B);{Ni2[dasa]2(H2O)2} (3B);{Ni[dasa](1,10-phen)2} (4B);[Zn2(dasa)2(2-ethylim i)2]n(5B). The above five crystal structures were analysised. 1B forms one-dimensional ch ain through the intramolecular hydrogen bonds; 2B,4B form distorted octahedron through the intermolecular forces; 3B forms plane quadrilateral by the formation of intermolecul ar; 5B forms two-dimensional structure by intermolecular hydrogen bonds. The representat ion complexes’thermal stability was determined. The results show that such a insoluble 1 igand as 9,10-dihydro anthracene-9,10-endo-α,β-succinic acid reaction temperature, the PH value, reaction time, cooling velocity have a significant impact, for the crystals’form ation.3.4,4’-isopropyldouble (2,6-phenoxyacetic acid) was selected as the first ligand to synthesize one crystal 1C and one powder 2C through zinc nitrate and cadmium nitrate. The ligand and the zinc ions forming coordination polymers (1C) was analysis. At the s ame time these two compounds were characterized by FT-IR.1C forms one-dimensional structure by intermolecular interactions forces. And the representation 1C of thermal stabil ity was studied.4.2-hydroxy-5-methylisophthalic acid was selected as the first ligand to synthesize o ne crystal 1d and one powder 2d with zinc nitrate and cadmium nitrate。And the 1D for ms three-dimensional cage-like structure. 1D’s fluorescent properties were studied at the s ame time.更多还原