【作者】 李萍；

【导师】 程清蓉；

【作者基本信息】 武汉工程大学 ， 化学工艺， 2015， 硕士

【摘要】 本论文以2,6-二甲酰基-4-取代苯酚和1,3-丙二胺为反应物,在金属离子的诱导作用下发生[2+2]缩合反应,合成了二苯氧基四氮大环金属配合物,再与1,4-bis(1,2,4-triazol-1-ylmethyl)benzene进行超分子自组装,设计合成了一系列从未报道过的一维链状超分子配位聚合物。采用红外光谱(IR)、及X-射线晶体衍射(X-ray)等方法对其结构进行了表征,并对聚合物1-5进行了性质研究包括(电化学性质、紫外可见吸收光谱、紫外可见漫反射吸收光谱),最后计算出相应的最高占有轨道HOMO和最低未占有轨道LUMO之间的能带间隙Eg。详细的配位聚合物类型如下(相关中间配体结构图如图Ⅰ):[Cu2L2(1,4-Bix)]ClO4 1;[Zn2L1(1,4-Bix)2](ClO4)2·8H2O 2;[Zn2L3(1,4-Bix)]ClO4·CH3CN 3;[Mn4L2(1,4-Bix)3]Cl2·8ClO4·6H2O4;[Mn2L3(1,4-Bix)2](ClO4)2·5H2O 5.主要的研究工作如下:1.合成足量的2,6-二甲酰基-4-取代苯酚,在金属离子的诱导作用下该醛与1,3-丙二胺发生[2+2]缩合反应得到三种席夫碱大环双核金属配合物,以所得到的三种金属配合物和1,4-bis(1,2,4-triazol-1-ylmethyl)benzene为原料制备出五种一维链状配位聚合物1-5。实验研究结果表明:配位聚合物1、2、3、5结构均为一维无限长分子链状,配位聚合物4为四核锰离子配位聚合物,两个锰离子的配位环境不同,呈四方锥结构和八面体结构,且大环分子呈现马鞍状构型;聚合物1中两个铜离子配位环境均呈四方锥型,聚合物3中两个锌离子配位环境同样呈四方锥型;聚合物2和5中大环中心锌离子和锰离子具有相似的配位环境,均为八面体构型。循环伏安法测定聚合物1-5的电化学性质,结果表明:聚合物1、2、5在-1.4 V到+1.4 V之间均出现两个还原峰、一个氧化峰,其中有一对氧化还原峰是准可逆的;聚合物3在-1.4v到+1.4v之间出现了两对准可逆的氧化还原峰;聚合物4在-1.4v到+1.4v之间出现一个还原峰,两个氧化峰,其中半波电位在-0.788v左右的一对氧化还原峰(mn(ii)mn(ii)/mn(Ⅲ)mn(ii))是准可逆的。紫外可见吸收光谱研究聚合物1-5的光学性质表明聚合物1、2、4、5在紫外区均有两个吸收峰,相比之下,聚合物3在紫外区有较多的吸收峰。紫外可见漫反射吸收光谱研究聚合物1-5的光学性质表明聚合物在紫外可见区有吸收。最后,分别计算出聚合物的能带间隙值eg。2.课题组以2,6-diformyl-4-r-phenol,1,3-丙二胺,高氯酸盐和4,4-联吡啶为反应物制备出三个一维分子链状超分子配位聚合物6-8。实验研究结果表明聚合物6-8结构均为一维无限分子链状,中心铜离子以及锌离子配位环境相同,均为略为畸变的八面体构型,且整个大环分子扭曲程度很小。循环伏安法同样对聚合物6-8的电化学性质进行了测定,实验结果表明:配位聚合物6-8在-1.4v到+1.4v之间均出现一个氧化峰,两个还原峰,其中一对氧化还原峰是准可逆的。紫外可见分光光度法测定了聚合物6-8的光学性质,实验结果表明:聚合物6-8在紫外区均出现两个吸收峰,其中在400nm左右的吸收峰较小。除此之外,还对聚合物6-8进行了紫外可见漫反射光谱的测定,结果表明6-8在紫外可见区有吸收。最后同样分别计算出聚合物的能带间隙值eg。图I配体结构图FigureⅠ the structure of ligand H2L1:R=CH3 H2L2:R=Cl H2L3:R=F更多还原

【Abstract】 In this paper, homodinuclear metal complexes of tetra-nitrogen macrocyclic ligands containing two phenoxide groups were obtained, which were the [2+2] condensation products of 1, 3-diaminopropane with 2, 6-diformyl-4-R-phenol(where R=Me, Cl, and F) in the presence of metal ions. Then A series of novel one-dimensional chain-like coordination polymers have been designed and synthesized with supermolecular self-assembly between the macrocyclic ligands and 1, 4-Bis(triazol-1-ylmethyl)benzene.These coordination polymers were characterized by infrared spectroscopy(IR), cyclic voltammetry(CV), UV-visible absorptions-pectrum(UV-Vis), diffuse reflectance spectroscopy(DRS). The corresponding band gap Eg was calculated between the highest occupied molecular orbital HOMO and the lowest unoccupied molecular orbital LUMO. The detailed coordination polymers are displayed as follows(the structures of relative ligands are given in Figure I): [Cu2L2(1,4-Bix)]ClO4 1;[Zn2L1(1,4-Bix)2](ClO4)2·8H2O 2; [Zn2L3(1,4-Bix)]ClO4·CH3 CN 3; [Mn4L2(1,4-Bix)3]Cl2 · 8ClO4· 6H2O4; [Mn2L3(1,4-Bix)2](ClO4)2·5H2O 5. The main research work was listed as following:Enough 2, 6-diformyl-4-R-phenol was synthesized as intermediates. Five one-dimensional chain coordination polymers 1-5 were obtained by the [2+2] condensation products of 2, 6-diformyl-4-R-phenol with 1, 3-diaminopropane in the presence of 1,4-Bis(triazol-1-ylmethyl) benzene and M(ClO4)2·6H2O. X-ray structure determination showed that the chain structure is formed from the macrocyclic structure coordinating two metal ions linked by 1, 4-Bis(triazol-1-ylmethyl)benzene molecules. The experimental results show that coordination polymers 1,2,3,5 exhibited an infinite one-dimensional chain structure while coordination polymer 4 exhibited tetranuclear manganese complex dimer. In coordination polymer 4, Mn2+ ions have the different coordination environment which can be regarded as tetragonal pyramid, octahedral respectively. In addition, Robson-type Schiff base macrocyclic complex exhibits saddle-like structure. In coordination polymer 1, Cu2+ ions have the same coordination environment which can be described as tetragonal pyramid. Similarly, Zn2+ ions in coordination polymer 3 also presented the same coordination polyhedron which can be regarded as tetragonal pyramid. In coordination polymer 2, Zn2+ ions have the same coordination polyhedron, namely octahedral. The coordination environment of Mn2+ ions in coordination polymer 5 is similar to that of 2. Cyclic voltammetry(CV) studies show that coordination polymers 1, 2 and 5 behave two reduction peaks and one oxidation peak. Among them, one pair of redox peak is quasi-reversible in the range of potential- 1.4 V~+1.4 V. Coordination polymer 3 behaves two pairs of redox peaks which are quasi-reversible in the range of potential- 1.4 V~+1.4 V. Coordination polymer 4 behaves one reduction peak and two oxidation peaks. Similarly, one pair of redox peaks(Mn(II)Mn(II) /Mn(Ⅲ) Mn(II)) at Half-wave potential-0.788 V are quasi-reversible in the range of potential-1.4 V ~ +1.4 V. UV-visible absorption spectrum(UV-Vis) studies show that coordination polymers 1, 2, 4 and 5 appear two absorption peaks in the ultraviolet region, in contrast, coordination polymer 3 in the ultraviolet region appears more absorption peaks in the ultraviolet region. Diffuse reflectance spectroscopy(DRS) studies show coordination polymers 1-5 exhibit absorption peaks in the UV-visible region. Finally, band gap Eg of the coordination polymers are calculated respectively.Coordination polymers 6-8 from research group were obtained by reaction of 2, 6-diformyl-4-R-phenol with 1, 3-diaminopropane in the presence of 4, 4-bipyridine and M(ClO4)2·6H2O. X-ray structure determination showed that coordination polymers 6-8 have an infinite 1-D molecular ladder motif composed of macrocyclic dinuclear copper complex with 4,4′-bipyridine molecules. The coordination polyhedron of each copper(II) ion in coordination polymers 6, 7 have the same coordination environment which can be described as octahedral and the coordination polyhedron of each zinc(II) ion in coordination polymer 8 also can be described as octahedral. So the entire macrocyclic molecules twisted slightly. Cyclic voltammetry(CV) studies show coordination polymers 6, 7 and 8 behave two reduction peaks and one oxidation peak. Among them, one pair of redox peak is quasi-reversible in the range of potential-1.4 V~+1.4 V. UV-visible absorption spectrum(UV-Vis) studies show that coordination polymers 6,7 and 8 appear two absorption peaks in the ultraviolet region, and all the absorption peaks are small at 400 nm. In addition, diffuse reflectance spectroscopy(DRS) studies show that coordination polymers 6,7 and 8 exist absorption phenomenon in the UV-visible region. Lastly, band gap Eg of the coordination polymers are calculated respectively.更多还原