基于氧化偶氮苯四羧酸配体构筑的配位聚合物的合成、结构与性质研究

发布时间：2018-06-10 14:34

本文选题：配位聚合物 + 晶体结构　；参考：《西南大学》2017年硕士论文

【摘要】：设计并合成具有新颖结构或优良性质的金属-有机配位聚合物是从事配位化学或晶体工程研究人员的热门课题之一。本论文利用氧化偶氮苯四羧酸配体和不同的含氮配体及过渡金属盐,通过改变反应条件制备具有良好磁性/荧光或具有较高孔隙率的新型金属-有机配位聚合物,同时进一步探索了配位聚合物自组装原理和化合物结构之间的关系。本论文以氧化偶氮苯四羧酸配体(H4aobtc = 3,3’,5,5'-氧化偶氮苯四羧酸)为主配体,通过改变含氮辅助配体、过渡金属、反应条件,设计合成了 10例新型配位聚合物。通过多种仪器测试,如元素分析、ICP、IR、单晶X-射线衍射分析和粉末X-射线衍射分析(PXRD),对其晶体结构进行表征,并对化合物的热稳定性(TG)、荧光或磁学特性进行了初步研究。1.利用氧化偶氮苯四羧酸配体(H4aobtc)与含氮配体4,4'-联吡啶以及钴、镍盐在水热条件下反应,共合成了 2例基于多核金属簇为SBUs(次级建筑单元)构造的三维高连接配位聚合物:[Co7(aobtc)3(bpy)2(μ3-OH)2(μ2-OH2)2(H2O)4]·4H2O(1)[Ni5(aobtc)2(bpy)2(μ3-OH)2(H2O)6]· 4H2O(2)化合物1是一例以六核钴金属簇作为14-连接点构筑的具有自穿特征的三维,(4,4,14)-连接的配位聚合物,拓扑标号为(46)2(45·6)(430·526·631·74)。据我们了解,在缠结领域中,化合物1代表目前具有自穿特征的最高连接的配位聚合物。化合物2和化合物1结构具有相似性,化合物2是以四核镍簇为10-连接节点,呈现三维,(4,4,10)-连接网络,具有(46)(45·5)(410·518·612·75)拓扑标号的配位聚合物。同时,在仅由氧化偶氮苯四羧酸配体和金属簇SBUs形成的结构骨架中,具有八面体空腔,[M(bpy)2]2+(M = Co(1),Ni(2))片段通过与金属簇连接占据在这些空腔中。2.基于上述发现,设计通过改变金属或更换不同的含氮配体,期望得到具有孔性的配位聚合物。通过调节实验条件,得到了六个具有相同骨架的微孔配位聚合物,有不同种类的含氮配体和不同数目的客体水分子占据着这六个化合物的空腔:[Zn3(aobtc)2]· H2bpyH2O ·(3)[Zn3(aobtc)2]· H2bpp· H2O(4)[Cd3(aobtc)2]·[Me2NH2]2·3H20(5)[Co3(aobtc)2]Himi· H30·3HO2(6)[Co3(aobtc)2]· H2bpp· H20(7)[Mn3(aobtc)2]· H2bpy·2H2O(8)化合物3-8都是以三核金属簇为SBUs作为8-连接点,展现了(4,8)-连接的flu(萤石拓扑,拓扑标号为:(46)2(412·612·84))网络。这六个化合物结构相似,但由于孔道中客体分子的不同,这六个化合物具有不同体积的空腔。如果移除客体分子,通过platon计算,化合物3-8的孔隙率都在30%以上。同时,对比化合物1,2和3-8,不难发现,通过提高作为SBUs的金属簇的核度,能有效构建具有更高连接的配位聚合物。这为我们进一步探索配位聚合物的定向自组装原理提供了一定的实验基础。3.为了构筑具有更高孔隙率的配位聚合物,用混合溶剂热取代水热,反应体系中不再加入含氮配体。在此反应条件下,合成了两例具有二维结构的配位聚合物:[Co3(Haobtc)2(H20)4]· 11H2O(9)[Mn3(Haobtc)2(DM A)2(H20)2]· 2H20(10)化合物9和10都是以三核金属簇作为6-连接点,形成了(3,6)-连接的二维kgd(拓扑标号:(43)2(46·66·83))层,二维层再通过分子间作用力形成三维结构。但由于二维层之间的堆积方式的不同,及化合物10部分溶剂参与配位,导致化合物9具有40.8%的孔隙率,而化合物10只有6%的孔隙率(客体水分子除去后)。
[Abstract]:The design and synthesis of metal organic coordination polymers with novel structures or excellent properties are one of the hottest subjects engaged in coordination chemistry or crystal engineering. In this paper, the oxidation azobenzene four carboxylic acid ligands and different nitrogen ligands and transition metal salts have been used to prepare good magnetic / fluorescence or tools by changing the reaction conditions. A new type of metal organic coordination polymer with high porosity was used to further explore the relationship between the self-assembly principle of the coordination polymer and the structure of the compound. In this paper, the azobenzene four carboxylic acid ligands (H4aobtc = 3,3 ', 5,5'- oxidized azobenzene four carboxylic acid) were used as the main ligands, and the nitrogen assisted ligands, transition metals, and reactions were changed. Conditions, 10 new coordination polymers were designed and synthesized. Through a variety of instrument tests, such as element analysis, ICP, IR, single crystal X- ray diffraction analysis and powder X- ray diffraction analysis (PXRD), the crystal structure was characterized, and the thermal stability (TG), fluorescence or magnetic properties of the compounds were preliminarily studied by.1. using oxidized azobenzene four carboxyl. Acid ligand (H4aobtc) and nitrogen ligand 4,4'- bipyridine and cobalt and nickel salts were reacted under hydrothermal conditions. A total of 2 three dimensional high connected coordination polymers based on the SBUs (bpy) 3 (bpy) 2 (bpy) 2 (3-OH) 2 (H2O) 2 (H2O) 4]. 4H2O (1) 2 (2) 2 (2) compounds were synthesized. 1 is a three-dimensional, (4,4,14) - connected coordination polymer constructed of a six nuclear cobalt metal cluster as a 14- junction, with a topological label of (46) 2 (45. 6) (430. 526. 631 74). According to our understanding, in the tangled field, compounds 1 represent the current coordination polymers with the highest connection of self penetrating characteristics. Compound 2 and compound 1 The structure is similar. Compound 2 is a 10- connecting node with a tetra nuclear nickel cluster, presenting a three-dimensional, (4,4,10) - connection network, with a coordination polymer with (46) (45. 5) (410. 518. 612. 75) topological labeling. In the structural skeleton formed only by the oxidation azobenzene four carboxylic ligand and metal cluster SBUs, there are eight facial cavity, [M (bpy) 2]2+ (M = Co). 1), Ni (2)) fragments are occupied in these cavities by connecting with metal clusters and.2. based on the above discovery. By changing metal or replacing different nitrogen ligands, a porous coordination polymer is expected to be obtained. By adjusting the experimental conditions, six microporous coordination polymers with the same bone frame are obtained, with different kinds of nitrogen ligands and different kinds of ligands. Different number of guest water molecules occupy the cavity of the six compounds: [Zn3 (aobtc) 2]. H2bpyH2O. (3) [Zn3 (aobtc) 2], H2bpp. H2O (4) [Cd3 (aobtc) 2]. For the 8- connection point, the (4,8) - connected flu (fluorite topology, topological marked as: (46) 2 (412. 612. 84)) network. The six compounds are similar in structure, but the six compounds have different volumes of cavity due to the difference in the guest molecules in the channels. If the guest molecules are removed, the porosity of the compound 3-8 is more than 30%. At the same time, comparing the compounds 1,2 and 3-8, it is not difficult to find that by improving the nucleation of the metal clusters as SBUs, the coordination polymers with higher connections can be effectively constructed. This provides a certain experimental basis for our further exploration of the principle of the directional self-assembly of the coordination polymers,.3. for the construction of a higher porosity of the coordination polymer. [Co3 (Haobtc) 2 (H20) 4]. 11H2O (Haobtc) [Mn3 (Haobtc) 2 (DM A) 2 (H20) 2]. 2H20 (10) compounds 9 and 10 both are connected by three nuclear metal clusters. Topological labeling: (43) 2 (46. 66. 83)) layer, and the two-dimensional layer forms a three-dimensional structure through intermolecular force. But because of the difference in the way of accumulation between the two layers and the participation of the 10 part of the compound, the compound 9 has the porosity of 40.8%, and the compound 10 has only 6% porosity (after the guest water molecules are removed).
【学位授予单位】：西南大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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