【作者】 刘霞霞；

【导师】 卢丽萍； 冯思思；

【作者基本信息】 山西大学 ， 材料化学， 2023， 博士

【摘要】 配合物因其结构多样、可设计性强、框架结构能与客体分子发生相互作用等优点在吸附和分离、质子导电、催化降解、发光传感等领域表现出巨大的应用潜力。本论文以构筑具有催化降解和荧光传感性能的芳香羧酸类配合物为研究目标,选择了两个刚性不同的芳香多羧酸化合物作为有机配体,采用水/溶剂热法合成了11个结构新颖的富d电子过渡金属配合物,并通过X射线单晶衍射对其结构进行了表征。进一步研究了具有d⁹电子构型的Cu（II）配合物在催化降解方面的应用,以及具有d¹⁰电子构型的Zn（II）和Cd（II）配合物在荧光传感方面的应用。同时分析与总结了配合物框架结构和性能之间的关系。主要研究内容及结果如下:（1）以6-（3′,4′-二羧基苯氧基）-1,2,4-苯三羧酸为有机配体,引入桥连含氮辅助配体,通过水热法合成了三个新型Cu（II）配合物1-3,用于催化降解亚甲基蓝（MB）。降解研究表明在H₂O₂存在下,配合物1-3均可作为非均相催化剂对弱碱/碱性溶液中的MB表现出高效且稳定的催化降解性能,降解速率常数分别为0.069,0.402和0.133min^-1。优异的降解性能归因于配合物1-3中金属铜离子活性位点与H₂O₂发生了类Fenton反应,以及有机连接体起到光天线的作用,吸收光产生了氧化空穴（h⁺）和还原电子（e^-）。此外,详细考察和分析了初始MB浓度、催化剂使用量、p H值、H₂O₂浓度等因素对降解MB的影响,结果表明这些因素对配合物1-3的降解性能有很大影响。（2）采用半刚性6-（3′,4′-二羧基苯氧基）-1,2,4-苯三羧酸和刚性3,5-二（3,4-二羧基苯基）吡啶,以及不同的含氮辅助配体与Cd（II）离子反应,合成得到五个结构新颖的发光配合物4-8。荧光传感研究表明:这些配合物均可以作为水介质中的荧光传感材料。其中配合物6-8能够通过荧光增强效应实现对Zn²⁺离子的定性和定量检测,检出限分别为89.5,67.6和26.1 n M。在检测体系中即使存在其它金属离子,配合物6-8仍对Zn²⁺离子表现出良好的识别能力。相比于半刚性芳香多羧酸配合物6和7,刚性芳香多羧酸配合物8具有更加优异的传感性能,说明通过调节有机配体可以有效提高配合物的传感性能。（3）利用刚性有机配体3,5-二（3,4-二羧基苯基）吡啶合成了具有良好热稳定性和p H稳定性的Cd（II）配合物9。基于配合物9框架结构的刚性和存在未配位的羧基氧原子,配合物9可作为潜在的镧系离子荧光传感材料。在能量传递机制的作用下,配合物9通过不同的传感行为实现了对水中La³⁺/Eu³⁺/Tb³⁺/Dy³⁺的定量检测,检出限分别达到0.44μM,0.11μM,1.20 n M和0.59μM。此外,进一步研究了具有相同主配体的配合物8对镧系金属离子的传感行为,结果表明配合物8对水中的Eu³⁺和Tb³⁺表现出高灵敏度,检出限分别为0.35μM和10.9 n M,稍逊色配合物9。配合物8和9传感性能的差异可归因于配合物框架结构与镧系离子能量转移效率的不同。基于对镧系离子的高灵敏度,配合物8和9可作为镧系离子传感的候选材料。（4）通过刚性3,5-二（3,4-二羧基苯基）吡啶与Zn（II）离子反应,同时引入邻菲罗啉（phen）/2,2′-联吡啶（2,2′-bipy）作为含氮辅助配体合成了两个具有优异荧光性质的配合物10和11。光致发光研究表明配合物10和11可作为猝灭型荧光传感材料检测微量的Cu²⁺离子,检出限分别为74.6 n M和301.7 n M,可满足实际检测需求。此外,配合物10和11在4-羟乙基哌嗪乙磺酸（HEPES）缓冲溶液中对Cu²⁺离子也具有出优异的荧光猝灭性能。值得注意的是,配合物10和11对实际水样中Cu²⁺离子的检测具有较好的准确性,表明配合物10和11是具有实际应用价值的荧光传感材料。更多还原

【Abstract】 Complexes have shown great potential applications in the fields of adsorption and separation,proton conduction,catalytic degradation,luminescence sensing and so on,due to their diverse structures,strong designability,and the ability of framework structure to interact with guest molecules.In this paper,two aromatic polycarboxylic acid compounds with different rigidity were selected as organic ligands,and 11 transition metal complexes with abundant d electrons were synthesized by aqueous/solvothermal methods,and their structures were characterized by X-ray single crystal diffraction.The applications of Cu（II）complexes with d⁹ electronic configuration in catalytic degradation and Zn（II）/Cd（II）complexes with d¹⁰ electronic configuration in fluorescence sensing were further explored.At the same time,the relationship between the framework structure and properties of the complexes was analyzed and summarized.The main research contents and results are as follows:（1）Three novel Cu（II）complexes 1-3 were synthesized by hydrothermal method for the degradation of methylene blue（MB）using 6-（3′,4′-dicarboxyphenoxy）-1,2,4-benzenetricarboxylic acid as organic ligand and bridging nitrogenated auxiliary ligands.In the presence of H₂O₂,complexes 1-3 exhibited efficient and stable catalytic degradation performance of MB in weak alkaline/basic solutions as heterogeneous catalysts,with rate constants of 0.069,0.402 and 0.133 min^-1,respectively.The excellent degradation performance was attributed to the Fenton-like reaction between the active sites of copper ions in complexes 1-3 and H₂O₂,and the organic linker acted as a photo-antenna,which absorbed light to generate oxidized holes（h⁺）and reduced electrons（e^-）.In addition,the effects of initial MB concentration,catalyst dosage,p H value and H₂O₂ concentration on the degradation of MB were investigated and analyzed in detail.The results showed that these factors had great influence on the degradation performance of complexes 1-3.（2）Five novel luminescent complexes 4-8 were synthesized by the reaction of semi-rigid 6-（3′,4′-dicarboxyphenoxy）-1,2,4-benzenetricarboxylic acid or rigid 3,5-bis（3,4-dicarboxyphenyl）pyridine,and different nitrogenated auxiliary ligands,as well as Cd（II）ions.The fluorescence sensing studies showed that these complexes can be used as fluorescence sensing materials in aqueous media.Among them,complexes 6-8 can achieve qualitative and quantitative detection of Zn²⁺ions by fluorescence enhancement effect,with detection limits of 89.5,67.6 and 26.1 n M,respectively.Even in the presence of other metal ions in the detection system,complexes 6-8 still showed excellent recognition ability for Zn²⁺ions.Compared with complexes 6 and 7 based on the semi-rigid aromatic polycarboxylic acid,complex 8 constructed by the rigid aromatic polycarboxylic acid exhibited better sensing performance,indicating that the sensing performance of the complex can be effectively improved by adjusting organic ligands.（3）The Cd（II）complex 9 with good thermal and p H stability was synthesized using the rigid organic ligand 3,5-bis（3,4-dicarboxyphenyl）pyridine.Complex 9 can be used as a potential lanthanide ions fluorescence sensing material due to its rigid frame structure and the presence of uncoordinated carboxyl oxygen atoms.Under the influence of energy transfer mechanism,complex 9 can quantitatively detect La³⁺/Eu³⁺/Tb³⁺/Dy³⁺in aqueous solution through different sensing behaviors,with detection limits of 0.44μM,0.11μM,1.20 n M and 0.59μM,respectively.In addition,the sensing behavior of complex 8 with the same main ligand for lanthanide metal ions was further investigated,and the results showed that complex 8 also exhibited high sensitivity to Eu³⁺and Tb³⁺in aqueous solution,with detection limits of 0.35μM and 10.9 n M,respectively,which was slightly inferior to complex 9.The difference in sensing properties of complexes 8 and 9 can be attributed to the differences in the energy transfer efficiency between the complex frame structure and the lanthanide ions.Due to their high sensitivity to lanthanide ions,complexes 8 and 9 can be used as candidate materials for lanthanide ions sensing.（4）Two complexes 10 and 11 with excellent luminescence properties were synthesized by the reaction of rigid 3,5-bis（3,4-dicarboxyphenyl）pyridine with Zn（II）ions and phenanthroline（phen）/2,2′-bipyridine（2,2′-bipy）as nitrogenated auxiliary ligands.The photoluminescence study showed that the complexes 10 and 11 can be used as quenched fluorescence sensing materials for quantitative detection of Cu²⁺ions,and the detection limits were 74.6 and 301.7 n M,respectively,which can meet the practical detection requirements.In addition,the complexes 10 and 11 also showed excellent fluorescence quenching performance for Cu²⁺ions in HEPES buffer solution.It is worth noting that complexes 10 and 11 have good accuracy in the detection of Cu²⁺ions in actual water samples,which indicates that complexes 10 and 11 are fluorescence sensing materials with practical application.更多还原