【作者】 魏璐璐；

【导师】 李林科；

【作者基本信息】 郑州大学 ， 无机化学， 2014， 硕士

【摘要】 近年来，定向的合成具有特定结构以及特殊性能的配合物已经引起了人们巨大的研究兴趣。配合物所具有的性能与它的金属中心离子、配体的性质以及结构类型有很大的关系。而基于含巯基和氮杂环类的配体(如：巯基咪唑、巯基噻唑、巯基三氮唑、巯基噁二唑等等)构筑的配位聚合物不仅具有新颖、灵活多变的拓扑结构，且在光学、离子交换、气体吸附、磁性材料、医药、催化制氢、纳米材料、生物蛋白等方面具有广阔的应用前景。因此，此类配体吸引了越来越多的化学工作者的研究。考虑到上述原因，我们设计合成了三种柔性巯基氮杂环的配体：1H-1,2,4-三氮唑-1H-1,3,4-噻二唑-5-硫酮(tmttH),5-(1,2,4-三氮唑-1-亚甲基)-4-氨基-3-巯基-1,2,4-三氮唑(a-tmttH)和5-(1,2,3-苯并三氮唑-1-亚甲基)-4-氨基-3-巯基-1,2,4-三氮唑(a-btttH),并结合5-(4-吡啶基)-1,3,4-噁二唑-2-硫酮(pytH)和4-氨基-3-(3-吡啶基)-1H-1,2,4-三氮唑-5-硫酮(3-apttH)作为对比。本论文主要包括以下三部分内容：一、利用配体tmttH与金属Cd(II)、Zn(II)、Co(II)、Ni(II)、Pb(II)和Hg(II)离子采用溶剂热的方法，得到六个具有新颖结构的配位化合物：具有两种不同类型的右手螺旋链的四重穿插的三维结构[Cd(tmtt)2]n(1),二维双分子层结构[Zn(tmtt)2]n(2),二维皇冠型结构[Pb(tmtt)2]n(3)，一维双螺旋链结构的[Ni(tmtt)2·(H2O)2]n(4)和[Co(tmtt)2·(H2O)2]n(5)，单核结构[Hg(tmtt)2](6)。利用X-ray单晶衍射仪确定了配合物1-6的晶体结构，并对这些配合物进行了红外、元素分析等表征。另外对配合物1-6的热稳定性以及配体、1-3和6的固体荧光性能进行了研究，并初步分析了金属离子的几何构型对晶体结构以及晶体结构对其热稳定性的影响。二、分别利用pytH,3-apttH, a-tmttH和a-btttH为主配体，对苯二甲酸为辅助配体，Cd(II)和Zn(II)为金属中心，采用溶剂热的方法，得到六个结构新颖的配合物7-12。用X-ray单晶衍射仪确定了它们的晶体结构。另外，对主配体以及六种配合物的热稳定性以及固态荧光性能进行了研究。发现配体与d10电子构型的金属离子配位后，荧光强度均有很大程度的增加。配合物[Cd2(pyt)2(bdc)·(H2O)]n·H2O (7)为2D双分子层结构，[Zn2(3-aptt)2(bdc)]n(8)为二维网状结构，[Cd4(3-aptt)4(bdc)2]n·8H2O (9)为二维梯子状结构，[Zn2(a-tmtt)2(bdc)]n(10)为二维网格状结构，[Cd2(a-tmtt)2(bdc)]n(11)和[Cd2(a-bttt)2(bdc)]n(12)为结构相似的三维结构。结果发现，在配合物7-12中，对苯二甲酸均参与了配位，并且在反应中是不可缺少的。三、利用合成的Cd配合物为前驱体，采用乙二醇和乙二胺为溶剂，通过溶剂热的方法，制备出了纳米级别的CdS粉末样品，并对它们进行了PXRD表征。研究发现，通过调节溶剂的比例发现并不能有效的控制CdS粉末的形貌。下一步我们将会研究溶剂的种类对CdS制备的影响并且希望可以对其光催化性能以及电化学方面的性质进行深一步的探索。更多还原

【Abstract】 In recent years, constructing the complexes with specific structures and propertieshas became increasingly popular. And the function of coordination compound isclosely related to its metal center ions, ligand properties and structure types.Metal-organic frameworks (MOFs) constructed from the ligands containingsulfhydryl-group or N-heterocycle (e.g. sulfhydryl imidazole, sulfhydryl triazole,sulfhydryl thiadiazole and sulfhydryl oxadiazole), not only have novel and flexibletopological structures, but have potential application in the fields of optics, ionsexchange, gas adsorption, magnetism, medicine, catalysis and nano materials.Therefore, this kind of ligand has attracted more and more chemists to research.For these reasons, we design and synthetize three flexible ligands:5-[(1H-1,2,4-triazol-1-yl)methyl]-1,3,4-thiadiazole-2(3H)-thione (tmttH),4-Amino-5-(1,2,4-trizole-1-yl)methyl-1,2,4-triazole-3-thione (a-tmttH),4-Amino-5-(1,2,3-benzotrizole-1-yl)methyl-1,2,4-triazole-3-thione (a-btttH), thentaking4-Amino-3-(3-pyridyl)-1H-1,2,4-triazole-5-thione (3-apttH) and5-(4-pyridyl)-1,3,4-oxadiazole-2-thione (pytH) as comparisons.The dissertation includes three parts as follows:1. Using tmttH as the ligand to self-assemble with metal ions Cd(II)、Zn(II)、Co(II)、Ni(II)、Pb(II) and Hg(II) under hydrothermal condition. We obtained six newcoordination complexes1-6: a four-fold interpenetrating3D framework [Cd(tmtt)2]n(1), a2D bilayer [Zn(tmtt)2]n(2), a2D crown-shaped network [Pb(tmtt)2]n(3),1Ddouble–helical chain structures [Ni(tmtt)2·(H2O)2]n(4) and [Co(tmtt)2·(H2O)2]n(5),and a mononuclear structure [Hg(tmtt)2](6). The crystal structures were confirmed bysingle crystal X-ray diffraction and revealed that the ligand tmttH has strongcoordinative abilities. And these complexes were determined by IR and elementaryanalysis. We also investigated the thermal stabilities of1-6and solid-statefluorescence properties of1,2,3,6, the ligand and discussed the influences of metalion to the structure of complex and structure to the thermal stability.2. By the use of pytH,3-apttH, a-tmttH and a-btttH as the major ligands, Cd(II) and Zn(II) ions as the metal centers, H2bdc as auxiliary ligand, we obtained six newcoordination complexes7-12under hydrothermal condition. We confirmed the crystalstructures by single crystal X-ray diffraction. The thermal stabilities and solid-statefluorescence properties of7-12were also investigated. Complexes[Cd2(pyt)2(bdc)·(H2O)]n·H2O (7) shows2D bilayer structure,[Zn2(3-aptt)2(bdc)]n(8)is2D network,[Cd4(3-aptt)4(bdc)2]n·8H2O (9) is2D ladder-like structure,[Zn2(a-tmtt)2(bdc)]n(10) presents2D grid network,[Cd2(a-tmtt)2(bdc)]n(11) and[Cd2(a-bttt)2(bdc)]n(12) possess similar3D structure. The results also indicated thatthe second ligand coordinate to metal centers and it is necessary in the process ofself-assembly of7-12.3. By using the cadmium complexes as the precursors, ethylene glycol and ethidenediamine as the mixture solvents, we got CdS samples. They were confirmed byPXRD. The structure and morphology of the powder could be controlled by adjustingthe ratio of the mixed solvents. Then we expect the photocatalytic properties andelectrochemical properties of the samples can be reaearched.更多还原