咪唑端基咔唑桥联配体的配位化学及其电化学性质研究

发布时间：2018-04-13 13:05

  本文选题：咔唑 + 咪唑　； 参考：《山东师范大学》2017年硕士论文

【摘要】：金属-有机框架是由金属为连接点,有机物为linker的超分子配位聚合物,具有多孔性。本文以咔唑为母体合成了一系列含氮杂环的弯折型刚性有机配体,研究了其与过渡金属的自组装的合成方法和结构调控规律,得到了8例配位化合物,通过X-射线单晶衍射、元素分析和红外等测试表征了它们的结构,并研究了部分化合物的功能化性质。Ⅰ.通过溶剂热法,利用以2,7-二溴咔唑为母体的有机配体L1、L2和L3分别与过渡金属Cd(Ⅱ)反应,组装得到3例结构稳定的配位化合物(化合物1、化合物2和化合物3),通过元素分析、红外、X-射线粉末衍射、热重分析和X-射线单晶衍射等手段表征了它们的结构,并研究了取代基对调控结构的影响。Ⅱ.利用以咔唑为母体,咪唑为端基有机配体L2、L3、L4和L5分别与Ni(OAc)_2·4H_2O通过溶剂热反应自组装得到4例未见文献报道的二维金属-有机框架(化合物4、化合物5、化合物6和化合物7)。该四例化合物同构且具有良好的电催化性质,它们分别与GC电极形成的复合电极材料在电催化水解产氧性质上有一定的效果。选取在中性缓冲液中电催化性能较好的化合物4,研究其在不同p H缓冲液下的电催化性能,可以发现化合物4在p H=6的缓冲液中有较好的电催化性能,并且可以持续利用长达18小时。Ⅲ.利用已合成的有机配体L2和苯二甲酸混配与Mn Cl_2·4H_2O在溶剂热条件下组装得到一例分子结构的配位化合物[Mn(C_(20)H_(17)N_5)_2(H_2O)_4]·2(C_8H_5O_4)·2(H_2O),该化合物是以二价锰金属为配位中心的六配位结构,参与配位的两个氮原子分别来自于两个有机配体L2的咪唑端基,四个氧原子来配位的水分子。弱的相互作用力在形成三维结构中有不可或缺的作用,其三维结构是分子是通过三种π-π作用和七种氢键形成的。同时,我们也对其热失重分析进行了表征。
[Abstract]:Metal-organic framework is a supramolecular coordination polymer with metal as junction point and organic matter as linker.A series of flexural rigid organic ligands containing nitrogen heterocycles were synthesized using carbazole as the parent. The synthesis method and structural regulation of the complexes with transition metals were studied. Eight coordination compounds were obtained by X-ray single crystal diffraction.Their structures were characterized by elemental analysis and IR, and the functionalized properties of some compounds were studied.Three structurally stable coordination compounds (compound 1, compound 2 and compound 3) were synthesized by solvothermal reaction with transition metal Cd2 and L3, respectively, using the organic ligands L1, L2 and L3, which were based on 2-dibromocarbazole, and were analyzed by elemental analysis.Their structures were characterized by infrared X-ray powder diffraction, thermogravimetric analysis and X-ray single crystal diffraction, and the effects of substituents on their regulatory structures were studied.Using carbazole as parent, imidazole as terminal organic ligand L _ 2N _ 3L _ 3L _ 4 and L _ 5 as terminal organic ligands, respectively, by solvothermal self-assembly with Ni(OAc)_2 4H_2O, four unreported two-dimensional metal-organic frameworks (compound 4, compound 5, compound 6 and compound 7) were obtained.The four compounds are isomorphic and have good electrocatalytic properties. The composite electrode materials formed with GC electrode have certain effect in electrocatalytic hydrolysis of oxygen.The electrocatalytic activity of compound 4 in neutral buffer solution was studied. It was found that compound 4 had better electrocatalytic activity in buffer solution of pH 6.And can be used for up to 18 hours.The two nitrogen atoms involved in the coordination come from the imidazole terminal group of two organic ligands L2 and the water molecules coordinated by four oxygen atoms.Weak interaction forces play an indispensable role in the formation of three-dimensional structures, which are formed by three kinds of 蟺-蟺 interaction and seven hydrogen bonds.At the same time, we also characterized the thermogravimetric analysis.
【学位授予单位】：山东师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4
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本文编号：1744617