【作者】 宋娟；

【导师】 胡怀明；

【作者基本信息】 西北大学 ， 材料化学， 2014， 博士

【摘要】 近年来,随着晶工程和超分子化学的迅速发展,设计合成具有新颖结构和优良性能的配位聚合物已成为现代配位化学的研究热点之一。本文以设计合成具有优良光学性能、磁学性能以及具有较高热稳定性的过渡/稀土金属配合物为目标,选用合成的四种不同的含吡啶基配体,与过渡金属(ZnⅡ、MnⅡ、CoⅡ、NiⅡ)和稀土金属离子(EuⅢ、TbⅢ、DyⅢ、 NdⅢ、YbⅢ、LaⅢ、GdⅢ、PrⅢ)反应,成功合成了四个系列28个不同维度的配合物,用X-射线单晶衍射分析了其单晶结构,通过元素分析、红外光谱等技术对配合物进行了表征,研究了所得配合物的光学性质、磁学性质,并进一步研究了其热稳定性。全文分为五章,主要内容简介如下：第一章：简要介绍超分子化学、晶体工程、配位聚合物的定义发展,阐述了配位聚合物的合成、影响配位聚合物合成的因素、配位聚合物的结构及配位聚合物的实际应用。第二章：设计合成配体2,6-双(2-吡嗪基)吡啶-4-甲酸(HL1),用此配体和过渡金属ZnⅡ在芳香族羧酸和脂肪族羧酸作为辅助配体的条件下,得到了9个配位聚合物(1-9),与稀土离子EuⅢ、TbⅢ、DyⅢ等反应得到了7个稀土配位聚合物(10-16),探讨了辅助配体和反应条件对配位聚合物结构的影响,对配位聚合物的光学性能和热稳定性进行了研究。第三章：改进参考文献的方法合成了配体2,6-双(2-吡嗪基)吡啶-4-对苯甲酸(HL2),用此配体和过渡金属离子ZnⅡ、MnⅡ在水热条件下合成了五个结构不同的配位聚合物(17-21),探讨了不同的反应条件对配合物结构的影响,结果表明,辅助配体、pH值、金属盐阴离子、反应物配比等因素对配合物的结构可以起到一定的调控作用。对配合物的光学性能和热稳定性也进行了初步的研究。第四章：设计合成了一个新颖的有机配体2,6-双(2-吡嗪基)-4,4’-联吡啶(L3),并用此配体在多羧酸为辅助配体的条件下,运用水热法得到了四个过渡金属ZnⅡ/MnII的配位聚合物(22-25),讨论了氢键相互作用及π-π相互作用在超分子结构自组装过程中的作用。第五章：改进参考文献的合成方法,运用克莱森缩合反应制得了一个双p-二酮配体2,6-双(3-噻吩基-1,3-丙二酮基)吡啶(H2L4),运用扩散法用此配体和过渡金属离子以及稀土金属离子反应,得到了三个3d-4f混配三螺旋金属配合物(26-28)。通过对配合物26和27的磁学性质研究发现,配合物中的过渡金属和稀土金属之间有反铁磁作用存在,此外对配合物的紫外可见以及PXRD和热稳定性进行了研究,研究表明配合物26-28是具有较高热稳定性的均相纯净配合物。更多还原

【Abstract】 With the rapid development of crystal engineering discipline and supramolecular chemistry, the design and synthesis of novel functional coordination polymers which have interesting and useful structure have been one of the most interesting research topics in coordination chemistry. The dissertation is aimed to synthesize transition and/or lanthanide coordination complexes with excellent photophysical or magnetic properties and good thermal stabilities. Four series,28transition and/or lanthanide coordination complexes are successfully designed by the reactions of transition metals (ZnⅡ、MnⅡ、CoⅡ、NiⅡ) and/or lanthanide ions (EuⅢ、TbⅢ、DyⅢ、NdⅢ、YbⅢ、LaⅢ、GdⅢ、PrⅢ) with four different kinds of derivatives of pyridyl derivative ligands. The coordination complexes are characterized by X-ray single crystal diffraction, elemental analyses, IR spectral analyses. Their luminescence properties and magnetism have been investigated, their thermal stabilities have also been studied. The dissertation includes the following five parts:Chapter1:The basic theory and concept of supramolecular chemistry, crystal engineering and coordination polymer are simply introduced. The synthesis of coordination polymer, the factors which affect the synthesis of coordination polymer, the structures of coordination polymers and the practical application of coordination polymers have also been briefly introduced.Chapter2:The2,6-bis(pyrazin-2-yl)pyridine-4-carboxylate (HL1) has been synthesized. Nine novel ZnⅡ coordination complexes (1-9) based on the HL1and aliphatic/aromatic carboxylic acid as auxiliary ligands have been synthesized successfully, and seven lanthanide coordination polymers (10-16) were also based on the HL1and lanthanide ions EuⅢ、TbⅢ、 DyⅢ etc. The influence factors of auxiliary ligands and reaction conditions have been discussed. The luminescence properties and the thermal stability of the coordination polymers have been also investigated.Chapter3:The ligand4-(2,6-di(pyrazin-2-yl)pyridine-4-yl)-benzoic acid (H2L) was synthesized according to a modified literature procedure. Five novel ZnⅡ/MnⅡ coordination polymers (17-21) with different structure have been hydrothermally synthesized. The influence factors of different reaction conditions have been discussed. The results is during the construction of the coordination polymers, the auxiliary ligands, pH values, the anions of the metal salts, molar ratio of the reagent, reaction temperature, et, have important influences on the final structures to some extent. The luminescence properties and the thermal stability of the coordination polymers have been also investigated. Chapter4:The ligand2,6-di(pyrazin-2-yl)-4,4’-bipyridine (L3) which has never been reported has been synthesized. Four novel transition metal (ZnⅡ, MnⅡ) coordination polymers (22-25) based on HL3and carboxylic acid as auxiliary ligands have been hydrothermally synthesized successfully. The hydrogen interactions and π-π stacking interactions play an important role on the constructing of supramolecular network.Chapter5:The ligand2,6-bis(3-thienyl-3-henylpropionyl)-pyridine (H2L4) was synthesized according to a modified literature procedure using the Claisen condensation reaction. Three novel3d-4f heterotrinuclear complexes with triple-helical architectures (26-28) have been synthesized successfully by the reactions of transition meta and lanthanide ions with H2L4. The research results of the magnetic properties of26and27support the existence of a ferromagnetic exchange interaction between the transition meta and lanthanide ions. In addition, the UV-visible spectra, the PXRD and the thermal stability of the coordination polymers have been also investigated and the results indicate the coordination polymers are pure and possess good thermal stability.更多还原