【作者】 王媛媛；

【导师】 岳琦；

【作者基本信息】 华东师范大学 ， 无机化学， 2021， 硕士

【摘要】 多孔金属有机骨架（MOFs）是一种具有与众不同的拓扑结构及孔径可调的多功能配位聚合物材料,在离子传输、成像、催化、气体存储及分离等方面大有可为。目前MOF合成手段较为成熟,据文献报道溶剂热法已经合成得到大量的MOF。所以本课题主要以溶剂热为合成手段,选择不同的手性有机配体作为主配体,通过辅助配体调节,和金属离子构筑手性MOF。通过文献阅读和课题组积累经验,本论文选择Cu²⁺,Co²⁺,Eu³⁺,Tb³⁺等金属离子和不同的混合配体构筑得到六种手性MOFs。运用X-射线单晶结构解析、粉末X射线衍射（PXRD）、圆二色、热重、红外等多种手段对配位聚合物的结构进行表征。并对部分配位聚合物进行染料选择性吸附、手性识别等性质研究,本论文的研究工作主要包含以下三个部分:一:1-单（L-丙氨酸）对苯甲酸与Zn²⁺、Co²⁺构筑的手性配合物利用主配体1-单（L-丙氨酸）对苯甲酸（H₂L1）,辅助配体bpee、bpea在不同条件下分别和与Zn²⁺,Co²⁺构筑得到配合物Y-1,Y-2。在主配体H₂L1与金属离子配位过程中,苯甲酸部分的羧基采取双齿桥连模式,丙氨酸部分的羧基采取双齿螯合模式,同时在辅助配体的调节下形成二维层,最后在分子间作用力的帮助下形成三维超分子结构。通过实验发现将辅助配体由bpea换为bpee时,结构相同的二维层状配位聚合物出现得染料吸附性能,bpea参与构筑的Y-1对染料没有吸附性,bpee参与构筑的Y-2对染料表现出良好的吸附选择性,对碱性阴离子染料甲基橙、刚果红可以快速选择吸附,通过PXRD表征发现Y-2在脱附甲基橙后骨架不变,证明其吸附性能稳定。而bpea参与构筑Y-1无法对染料吸附。二:1,4-双（L-脯氨酸）对苯甲酸与Cu²⁺构筑的手性配合物利用主配体1,4-双（L-脯氨酸）对苯甲酸,辅助配体bpea、bpee在不同条件下与Cu²⁺构筑得到三维配合物Y-3,Y-4。Y-3及Y-4均是由金属与手性主配体形成的不同螺距的左手螺旋链与辅助配体形成的左手螺旋链编织而成的3D配位聚合物。在Y-3中,Cu²⁺离子与手性配体和bpea形成同种左手螺旋链。不同的是,在Y-4中,Cu²⁺离子与手性配体形成了四种不同类型的左手螺旋链,Cu²⁺离子与bpee配体形成的左手螺旋链将四种螺旋链串连在一起。由于Y-4中存在辅助配体bpee,我们探究了Y-4对染料的选择性吸附,发现其仍然能对碱性阴离子染料有选择性吸附,但无法通过浸泡等方式脱附吸附物。实验证明了染料的选择性吸附性能与金属离子无关,而与结构和bpee配体的存在有着密切的关系。此外,由于Y-4中存在双螺旋结构,于是我们探究了其对手性氨基酸的响应能力,通过紫外分光光度计可发现L/D-色氨酸与Y-4相互作用,能使色氨酸的紫外吸收的信号增强,但无法识别光学异构体的氨基酸;故而进一步借用电化学工作站对其进行循环伏安曲线的测定,发现可通过电化学的方法利用Y-4对D/L色氨酸进行手性识别。三:1-（L–脯氨酸）对苯甲酸与Tb³⁺、Eu³⁺构筑的手性配合物利用主配体1-（L–脯氨酸）对苯甲酸,辅助配体1,10-phen在溶剂热下与稀土金属Eu³⁺、Tb³⁺构筑的到配合物Y-5,Y-6,主配体在Y-5及Y-6中配位方式相同。手性配体连接稀土离子形成一个二维层状聚合物,辅助配体1,10-phen在其中起到调整连接方向的作用,由于稀土离子的镧系收缩效应,故而Y-5/Y-6结构相同,且通过荧光分析发现二者是潜在的发光材料,可用作荧光探针。更多还原

【Abstract】 The Porous Metal-Organic Framework（MOF）is a type of multifunctional polymer material with a distinctive topology structure and adjustable aperture diameter.They are promising in ion transport,imaging,catalysis,gas storage and separation.Currently,the method of synthesizing MOF is very ripe.According to literature reports,a large amount of MOF has been synthesized by solvothermal method.Therefore,this topic mainly uses solvothermal as the synthesis method,chooses different chiral organic ligands as the main ligand,adjusts by auxiliary ligands,and constructs a chiral MOF with metal ions.In this paper,we reviewed the research team’s literature and expertise and selected metal ions such as Cu²⁺,Co²⁺,Eu³⁺,Tb³⁺and different mixed ligands to construct six chiral MOFs.It also includes a subset of other properties such as polymer adsorption,chiral identification,and creative structural analysis,radiographic analysis（PXRD）,temperature analysis,cycle dichroism,and infrared.The research of sex recognition and other properties.The explore content is divided into three parts:1:1-mono（L-alanine）p-benzoic acid and Zn²⁺,Co²⁺chiral complexesUsing the main ligand 1-mono（L-alanine）p-benzoic acid（H₂L1）,the auxiliary ligands bpee and bpea were self-assembled with Zn²⁺and Co²⁺under different conditions to obtain complexes Y-1,Y-2.When the chiral ligand H₂L1 independently assembles with metal ions,the carboxyl group of the benzoic acid part adopts the double bridging mode,and the carboxyl group of the alanine part adopts the double chelate mode.At the same time,it forms a two-dimensional layer under the adjustment of the auxiliary ligand.The layer bilateral ultimately implements the supramolecular structure of 3D support integration.It is found through experiments that when the auxiliary ligand is changed from bpea to bpee,the two-dimensional layered coordination polymer with the same structure has dye adsorption performance.The Y-1 constructed by bpea has no adsorption to the dye,and the Y-2 constructed by bpee participates in the construction.Y-2 shows good adsorption selectivity for dyes.It can quickly and selectively adsorb the basic anionic dyes methyl orange and Congo red.The PXRD characterization shows that the skeleton of Y-2 does not change after desorption of methyl orange,which proves its adsorption performance stable.But bpea participates in the construction of Y-1 and cannot absorb dyes.2:A chiral complex constructed by 1,4-bis（L-proline）p-benzoic acid and Cu²⁺Using the main ligand 1,4-bis（L-proline）p-benzoic acid,and the auxiliary ligands bpea and bpee with Cu²⁺under different conditions,constructed 3D coordination polymer Y-3 and Y-4.Both Y-3 and Y-4 are 3D coordination polymers formed by woven left-handed spiral chains of different angles formed by metal and chiral main ligands and spiral chains of left hand formed by accessory ligand,respectively.In Y-3,Cu²⁺ions,chiral ligands and bpea form simple spiral chains of left hand.The difference is that in Y-4,Cu²⁺ions and chiral ligands form four different types of left-handed helical chains,and the left-handed helical chains composed of Cu²⁺ions and bpee ligands connect the four spiral chains together.Because of the auxiliary ligand bpee in Y-4,we explored the selective adsorption of dyes by Y-4,and found that it can still selectively adsorb basic anionic dyes,but cannot desorb the adsorbate by means such as soaking.Experiments have proved that the selective adsorption performance of the dye has nothing to do with metal ions,but has a close relationship with the structure and the existence of bpee ligand.In addition,due to the double helical structure in Y-4,we explored the responsiveness of its chiral amino acids.The UV absorption signal of the chromophore is amplified,but the amino acid of the optical isomer cannot be recognized.Therefore,the cyclic voltammetry curve of Y-4 was measured by an electrochemical workstation,and it was found that Y-4 can be used for chiral identification of D/L tryptophan by electrochemical methods.3:Chiral complexes of 1-（L-proline）-benzoic acid with Tb³⁺and Eu³⁺Using the main ligand 1-（L-proline）-benzoic acid,the auxiliary ligand 1,10-phen and the rare earth metals Eu³⁺and Tb³⁺under solvothermal build up to the complexes Y-5,Y-6,the main ligand The coordination mode of the body is the same in Y-5 and Y-6.The chiral ligand connects the rare earth ions to form a two-dimensional layered polymer.The auxiliary ligand 1,10-phen plays a role in adjusting the connection direction.Due to the lanthanide shrinkage effect of the rare earth ions,Y-5/Y-6 The structure is the same,and through fluorescence analysis,it is found that the two are potential luminescent materials,which can be used as fluorescent probes.更多还原