唑类配体的刚性和柔性对配位聚合物结构和性质的影响

发布时间：2018-06-03 15:08

  本文选题：配位聚合物 + 1　； 参考：《西北大学》2017年硕士论文

【摘要】：近二十年来,配位聚合物一直保持着长盛不衰的发展势头,不仅结构越来越变化多样,并且在光、电、磁、热、医药学、生物等许多领域展示着不可估量的实际应用价值。如何设计得到所希冀的拥有独特结构和卓越性能的目标配合物,是近年来科学家们始终致力于攻克的难题。本论文选取典型的柔性的双咪唑配体1,6-二(2-甲基咪唑)己烷(bimh)和典型的刚性的三吡唑配体1,3,5-三吡唑苯(tpb)作为主配体,构筑了 15例结构不同的配位聚合物,来探索配体的刚性和柔性对配合物结构和性质的影响。论文一共分为四个部分:第一部分为绪论,首先简单的介绍了配位化学、配位聚合物的概念,配合物的合成方法以及影响配位聚合物结构的因素。然后,介绍了近几年配位聚合物在热动力学从理论到实践方面的应用。其次,对柔性咪唑类配合物和刚性吡唑类配合物的实验研究背景和进展作了简要概述,对本论文的选题依据及意义做了简单的介绍。第二部分选取柔性的1,6-二(2-甲基咪唑)己烷(bimh)和几种羧酸,过渡金属作为中心金属,使用溶剂热合成法,构筑了 8个功能配合物:[Zn(bimh)0.5(5-MIPA)]_n(1),[Cu(bimh)0.5(1,4-H_2ndc)]_n(2),{[Co5(bimh)_2(H_2bdc-Br2)4]·3H_2O}n(3),{[Co2(bimh)0.5(5-TBIPA)_2]}n(4),{[Zn_2(bimh)1.5(5-TBIPA)_2]}n(5),{[Ni(bimh)(5-NIPA)]·EtOH}n(6),{[Zn_3(bimh)0.5(5-NIPA)_2]·2H_2O }n(7),[Cd(bimh)(5-NIPA)]_n(8)。对这 8 例配合物中的bimh配体的空间构象进行了分析讨论。对它们进行了元素分析(EA)、粉末衍射(PXRD)、红外光谱(IR)等组成和结构表征以及荧光性质和TG/DTG-DSC热动力学表征和讨论,分析了配合物的热稳定性。第三部分选取刚性的1,3,5-三吡唑苯和芳香竣酸作为混合配体,过渡金属为中心金属,通过水热合成法,构筑了 7个配位聚合物:[Ni(tpb)_2(2,2'-TDA)_2]_n(9),[Cd_2(tpb)_2(H_2IPA)_2]_n(10),[Zn_2(tpb)(H_2TPA)]_n(11),[Co(tpb)(2,2'-dpa)]_n(12),[Ni(tpb)_2(H_2tpa-OH_2)]_n(13),{[Zn(tpb)(5-OIPA)]H_20}n(14),[Cu(tpb)(H_2bdc-C12)]_n(15)。与论文第二部分相同,对这7例配合物的结构和性质进行了测试和分析。第四部分为论文的总结和讨论。
[Abstract]:In the past 20 years, coordination polymers have maintained the momentum of development. Not only the structure is more and more diverse, but also in many fields such as light, electricity, magnetism, heat, medicine, biology and so on, it shows inestimable practical application value. How to design the desired target complexes with unique structure and excellent performance has been a difficult problem for scientists in recent years. In this paper, 15 cases of coordination polymers with different structures were constructed by using typical flexible bis (imidazole) ligands (1: 6-dimethylimidazole) hexane (bimh) and rigid tripyrazole ligands (1-3-5-tripyrazolyl benzene tpb) as main ligands. To explore the effects of ligand rigidity and flexibility on the structure and properties of the complexes. The thesis is divided into four parts: the first part is introduction. Firstly, the coordination chemistry, the concept of coordination polymer, the synthesis method of coordination compound and the factors affecting the structure of coordination polymer are introduced briefly. Then, the applications of coordination polymers in thermodynamics from theory to practice in recent years are introduced. Secondly, the experimental background and progress of flexible imidazole complexes and rigid pyrazole complexes are briefly summarized, and the basis and significance of this thesis are briefly introduced. 绗�浜岄儴鍒嗛�夊彇鏌旀，

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