新颖金属有机配位型荧光与光色材料的设计合成与性能表征

发布时间：2018-06-19 03:24

本文选题：光敏配位化合物 + 荧光-光色材料　；参考：《华南理工大学》2016年硕士论文

【摘要】：化合物对光、热和机械压力等外界刺激产生相应的荧光变化的特性,可用于设计与制备荧光分子开关、传感器、显示器和光储存设备等器件所需的荧光调制材料。近来,探讨分子的修饰、分子结构的设计、分子间相互作用以及不同外界刺激对物质荧光调控方面的研究,倍受国内外研究者的关注。本文以大环多配位点荧光配体PYTPY作为吸收光能的触角和发射荧光的主要基团,通过配体和金属的配位来实现化合物结构的调控,制备了系列具有不同结构的配位基荧光分子材料,并对其开展结构、热稳定性、荧光与光色、红外与紫外等光谱的表征。所取得的具体研究结果如下:1.通过配体基团的设计,调控其配合物的结构、与荧光等物化特性。已设计和制备三种大环荧光配体,其中PYTPY(4'-(4-吡啶基)-2,2':6',2''-三联吡啶)配体的端基为缺电子的吡啶环,可在配位化合物中作为电子受体;DMATPY(4′-(4-N,N′-二甲氨基苯基)-2,2′:6′,2″-三联吡啶)的端基为富电子的二甲氨基,是很好的荧光探针材料;CPTPY(4′-(4-羧基苯基)-2,2′:6′,2″-三联吡啶)的端基为羧基,含有N,O两种配位原子,可用于与不同金属配位构建多结构配位分子体系。2.以PYTPY为电子受体,利用水热法中DMF分解产生的甲酸为电子给体,与镉离子配合构建了一例荧光调制型D-A光色配位化合物Cd(NO_3)(HCOO)(H_2O)(PYTPY)(1)。该分子的密堆积结构导致其可构成固体光激激基缔合物。在光照的条件下,化合物1展示出有趣的荧光调制和光色变化现象,为一例有趣的配位基光敏分子体系。3.以PYTPY为电子受体,Cl离子为电子给体,与镉原子配合构建了一例荧光D-A配位化合物CdCl_2(PYTPY)(2)。化合物2的晶体结构中给受体分子间的距离较远,固态无光激激基缔合物特性。将其溶于溶液中,随着给受体间的分子间距离缩小,其可展现出同上例光激激基缔合物类似的现象。以PYTPY为配体,在其端基吡啶氮参与配位的条件下,构建一例双核镉氯簇层状超分子结构Cd_3Cl_6(PYTPY)_2(3),该化合物的荧光在外力的作用下可发生由弱到强的变化,展示出有趣的碾磨机械调制荧光现象。4.以DMATPY和CPTPY为荧光配体合成的小分子CdCl_2(DMATPY)(4)和Zn(CPTPY)_2(5)。由于其配体的富电子性,以其构建的配位化合物与需探测的金属离子之间可发生较强的相互作用。此类配体与金属离子间的拉电效应致的荧光迁移特性可用于探测不同离子的存在与浓度。
[Abstract]:The properties of the compounds to the external stimuli, such as light, heat and mechanical pressure, can be used to design and fabricate fluorescent modulating materials for devices such as fluorescent molecular switches, sensors, displays and optical storage devices. Recently, researches on molecular modification, molecular structure design, intermolecular interaction and the regulation of substance fluorescence by different external stimuli have attracted much attention from researchers at home and abroad. In this paper, the macrocyclic multi-coordination point fluorescence ligand PYTPY is used as the main group for absorption of light energy and emission fluorescence, and the structure of the compound is regulated by the coordination of ligand and metal. A series of coordination group fluorescent molecular materials with different structures were prepared and characterized by their structure, thermal stability, fluorescence and light color, IR and UV spectra. The specific results obtained are as follows: 1. 1. Through the design of ligand group, the structure of its complex and its physicochemical properties such as fluorescence were regulated. Three macrocyclic fluorescent ligands have been designed and prepared, in which the end group of PYTPYC4O4-PYTPYO4-PYTPYO4-PYTPYO4- 4- pyridyl ~ (2 +) (2: 6) is an electron-deficient pyridine ring, and the end group of the ligands is electron-deficient pyridine ring. In the coordination compound, the terminal group of the electron acceptor, DMATPYO4 (4) -N (N) -dimethylaminophenyl (2) (2 "), is electron-rich dimethylamino (DMTA), which can be used as an electron acceptor in the coordination compound, and can be used as an electron acceptor. It is a very good fluorescent probe material, CPTPYO4, 4-carboxyl-phenyl-2-tripyridine), the terminal group of which is carboxyl group and contains two kinds of coordination atoms. It can be used to coordinate with different metals to construct multi-structure coordination molecule system. Using PYTPY as electron acceptor and formic acid decomposed from DMF in hydrothermal process as electron donor, a fluorescent modulated D-A photochromic coordination compound CDNO _ 3 was constructed by using CD ~ (2 +) ~ (2 +) as an electron donor. The dense stacking structure of the molecule leads to the formation of a solid photoexcited group association complex. Under light condition, compound 1 exhibits interesting fluorescence modulation and photochromatic variation, which is an interesting ligand Guang Min system. 3. Using PYTPY as electron acceptor Cl ion as electron donor, a fluorescent D-A coordination compound CdCl2PYTPYPYYPU was constructed with cadmium atom. The distance between the acceptor molecules in the crystal structure of compound 2 is relatively long, and the characteristics of the solid-state light-free excimer association complex. When it is dissolved in the solution, the similar phenomenon of photoluminescent association complex can be shown as the distance between the donors decreases. Using PYTPY as ligand, a binuclear cadmium chloride cluster with layered supermolecular structure CD _ 3Cl _ 6 / PYTPY _ 2 was constructed under the condition that its terminal pyridine nitrogen participated in the coordination. The fluorescence of this compound can change from weak to strong under the action of external force. Show interesting milling machine modulation fluorescence phenomenon. 4. DMATPY and CPTPY were used as fluorescent ligands. Due to its electron-rich ligands, there is a strong interaction between the coordination compounds and the metal ions to be detected. The fluorescence migration characteristics of the ligand and metal ions can be used to detect the existence and concentration of different ions.
【学位授予单位】：华南理工大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O641.4

【相似文献】