手性联苯酚类In-MOF的设计、组装与性能研究

发布时间：2018-01-12 04:30

本文关键词：手性联苯酚类In-MOF的设计、组装与性能研究　出处：《上海师范大学》2015年硕士论文　论文类型：学位论文

【摘要】：手性的金属-有机晶态框架多孔材料因其在多相不对称催化、手性识别分离以及手性传感等领域广泛应用而成为基础材料化学的研究热点之一。本论文使用具有C2轴对称性的手性联苯酚小分子化合物作为基本骨架单元,设计并合成出羧酸官能化的手性的联苯酚有机桥联配体,通过与金属铟离子组装构筑出具有结构稳定、性能优异的手性的金属有机晶态框架多孔材料。该材料的基本结构经X-射线单晶衍射、元素分析、红外、热重等多种常规表征方式确定,并对其在手性识别与分离、手性荧光传感、手性诱导结晶等方面进行了性能探索研究。本论文分为以下四章:第一章,首先简要介绍了手性的金属-有机晶态框架多孔材料的研究现状,包括手性的金属-有机晶态框架多孔材料的合成方法以及其在手性识别与分离、多相不对称催化、手性传感等方面应用;其次对论文的选题意义以及工作进展做了概述;第二章,设计并合成出一种具有C2轴对称性的手性的有机桥联联苯酚配体分子H4L((R)-3,3’,5,5’-四(对羧基苯基)-6,6’-二甲基-1,1’-联苯-2,2’-二酚),将其与金属铟离子成果地构筑出一个具有一维纳米孔道的手性的金属-有机晶态框架材料(R)-In-MOF。该框架材料经TGA、CD、PXRD以及BET和N2吸附曲线等常规谱学表征。第三章,(R)-In-MOF作为一种性能良好的固态吸附剂能够选择性地吸附并分离外消旋芳香类亚砜化合物,其拆分ee值最高可达97.7%。同时该手性的框架材料可以进行回收利用,并且进行多次循环使用后该材料的拆分效果相当;利用手性的In-MOF研究了其在溶液中对一系列糖类化合物的手性荧光识别,其最高的选择性可达5.82±0.18;另外(R)-In-MOF还可以作为一种手性诱导媒介,可以诱导饱和外消旋丙氨酸溶液结晶,其立体选择性最高可达93%ee。第四章,对本论文工作进行了总结展望。
[Abstract]:Chiral metal organic framework materials because of its porous crystalline in heterogeneous asymmetric catalysis, chiral recognition and chiral separation of sensing and other fields are widely used and become one of the hot research foundation of material chemistry. This thesis used Chiral Biphenyl phenolic small molecular compounds with C2 axis symmetry as the basic skeleton unit, the design and synthesis of chiral carboxylic acid the functionalized xenol organic bridging ligands and metal ions, through the assembly of indium stable structure, crystalline porous metal organic framework materials with excellent properties. The basic structure of the chiral materials by X- ray diffraction, elemental analysis, IR, TGA to determine various conventional representations, and the chiral the recognition and separation of chiral fluorescent sensor, studied the properties of chiral induced crystallization and so on. This paper is divided into four chapters: the first chapter briefly introduces the hand Research status of organic crystalline porous materials of metal framework, including synthetic methods of chiral metal organic framework crystal porous material and the chiral recognition and separation, heterogeneous asymmetric catalysis, chiral sensing applications; secondly, the significance of the topic and the progress of the work is summarized; the second chapter, the design and synthesis a kind of chiral organic bridging with C2 symmetry of the xenol ligand H4L ((R) -3,3, four '5,5' - (4-carboxyphenyl) -6,6 '- two' - methyl -1,1 '- biphenyl -2,2, two phenol) with the metal indium ion results to construct a one dimensional nano pore chiral metal organic framework crystal materials (R) -In-MOF. the frame material by TGA, CD, PXRD, BET and N2 adsorption curve of conventional spectroscopic characterization. In the third chapter, (R) -In-MOF solid as a good adsorbent can adsorb selectively And the separation of racemic aromatic sulfoxide compounds, its resolution EE value up to 97.7%. at the same time, the framework material of chirality can be recycled, and repeatedly split the effect of the use of materials is studied; the column fluorescent chiral carbohydrate recognition of a system in solution using chiral In-MOF, the highest the selectivity of 5.82 + 0.18; and (R) -In-MOF can also be used as a chiral induction medium can induce the crystallization of racemic alanine saturated solution, the stereoselectivity of up to 93%ee. in the fourth chapter, the work of the thesis are summarized.

【学位授予单位】：上海师范大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB383.4;O627

【共引文献】