【作者】 赵慧；

【导师】 胡怀明；

【作者基本信息】 西北大学 ， 物理化学， 2017， 硕士

【摘要】 配位聚合物具有多种多样的成键方式、丰富多彩的空间构型和独特的物理、化学性质,在科学研究以及生活方面已有非常多的应用。特别是近年来许多配合物在通信,信息处理、传感、转换,材料,生物等领域展现出的独特的功能,成为了一类富有现实意义的功能性配合物。以功能性配合物为基础可以组装成具有更丰富的物理特性的分子材料和纳米材料,并为聚集体纳米材料分子器件和分子机器打下了基础。本论文以合成具备新颖、独特的骨架结构和良好性质如:传感性质、发光性质的稀土金属配合物为目的,选用两种双功能的Phen的衍生物配体H3sfpip和HL,与稀土金属离子(LaⅢ-YbⅢ,YⅢ)反应,成功合成了 8种类型共30个的稀土金属配合物。利用X-射线单晶衍射对配合物的结构进行解析、利用红外、元素分析对配合物的化学键、官能团和元素做进一步确认、利用PXRD对这些配合物纯相进行检测。研究了所有配合物的发光性质以及部分配合物的传感性质。论文分为三部分共三章,对各部分内容做如下简介:第一章主要陈述了稀土金属配位聚合物的研究背景和研究意义,稀土金属离子的配位特性和稀土金属配合物的光学特性,并总结了近几年来稀土金属咪唑并邻菲罗啉衍生物配合物的研究现状。第二章选用配体H3sfpip,辅助配体草酸、丁二酸、己二酸与稀土金属离子在水热条件下成功构筑了 4个系列共17个配合物(1-17)。详细分析了每个系列配合物的结构并探讨了反应条件以及第二配体对于构筑配合物的影响。测试了 1-17的热重和荧光。研究结果表明H3sfpip能够有效地吸收能量并敏化稀土离子EuⅢ离子和TbⅢ离子发光。基于15优异的光学性质,对其传感性质做了进一步研究,研究表明配合物15能够高选择性、高灵敏度、可重复利用的选择性识别硝基苯,并且识别信号是肉眼可见的,最后还研究了硝基苯猝灭荧光的机理。第三章利用稀土金属离子与主配体HL,辅助配体己二酸,通过改变反应物的化学计量比和pH水热条件下成功合成了 3个系列共13个稀土配合物(18-30)。详述了 3种类型配合物的结构,讨论了反应条件对配合物的合成及结构的调控作用。荧光和热重分析表明18-30都有优异的发光性能和良好的热稳定性。此外,还利用物理掺杂的方法对EuⅢ/TbⅢ的化合物进行了掺杂,并且得到了白光发射。更多还原

【Abstract】 Coordination polymers have been widely used during the past few years because of their diversified bonding modes,fantastic space configurations and unique physical properties.Especially many coordination polymers show unique functions in the fields such as optical,magnetic,biological and electrical,which makes it become a kind of functional complexes with practical significance.Based on functional complexes,it can be assembled into molecular materials and nanomaterials with richer physical properties and lay the foundation for aggregated nanomaterials molecular devices and molecular machines.The thesis is aimed at constructing lanthanide coordination polymers which possess favorable thermostability,sensing and luminescence.The thirty lanthanide coordination polymers are successfully designed and synthesized by the reactions of bifunctional imidazophenanthroline derivative ligands with rare earth metal ions(LaⅢ-YbⅢ,YⅢ).Through X-ray analytical each class was described in detail the structure of the complexes,and through IR,element analysis for further characterization was carried out,through the powder diffraction to determine the purity of complexes.The thermal stability and fluorescence properties of each polymer were investigated,as well as sensing properties of a certain compound.The text is divided into the following three chapters:Chapter 1:Mainly summarized the research significance of rare earth metal coordination polymers,the coordination characteristics of rare earth metal ions and the optical properties of lanthanide coordination polymers.Reviews on the research progress of rare earth metal coordination polymers based on imidazophenanthroline ligand.Finally,the selected topic basis and research significance of this paper were elaborated.Chapter 2:Four types,seventeen rare earth coordination polymers(1-17)based on H3sfpip and oxalic acid,succinic acid,adipic acid as auxiliary ligands were synthesized.The structures of the coordination polymers were depicted in detail and the effects of auxiliary ligands and reaction conditions on constructing polymers were discussed.The fluorescence and thermostability properties of 1-17 were researched.Results indicate that H3sfpip can absorb energy efficiently and sensitization EuⅢ and TbⅢ.Sensing study reveal that 15 as luminescence sensor for detecting NB possesses the characteristic of high selectivity,high sensitivity,good reproducibility ability and the fluorescence response signals can be distinguished by naked eye under 365nm UV light irradiation.The quenching mechanism have been discussed in the end.Chapter 3:Three types,thirteen rare earth coordination polymers(18-30)based on HL and adipic acid as auxiliary ligands have been successfully synthesized by changing the stoichiometric ratio and pH value of the reactants.The structures of the coordination polymers were depicted in detail and the effects of reaction conditions on constructing polymers were discussed.The properties of 18-30 were also researched,and the results indicate that 18-30 have excellent luminescence properties and thermal stabilities.In addition,white light emission was realized by precisely tuning the mixing molar ratio of EuⅢ/TbⅢ compounds and change the excitation wavelength.更多还原