取代苯卟啉锡及N-错位卟啉苯卟啉的合成、表征与性质研究

发布时间：2018-11-08 20:06

【摘要】：卟啉以及金属卟啉,一直是有机合成的热点之一。金属卟啉锡的锡原子通过氧原子可与多种亲电基团结合形成多种类型的轴向配位卟啉化合物。已被广泛用作生物医学药物、催化剂以及纳米材料。本文主要设计合成了21种取代苯卟啉锡和10种N-错位苯卟啉化合物,通过红外光谱、核磁共振氢谱、元素分析、单晶X-射线衍射等技术表征了其结构,并初步研究了它们的结构自组装、紫外-可见吸收光谱、荧光光谱、电化学等性质。利用自制的5,10,15,20-四(4-氯苯基)卟啉化合物(A_1)、5,10,15,20-四(4-甲氧苯基)卟啉(A_(11))、5,10,15,20-四(4-叔丁苯基)卟啉(A_(21))卟啉化合物分别与氯化亚锡反应,合成了相应的苯卟啉氯化锡。水解后得到苯卟啉氢氧化锡。使用不同的有机酸(水杨酸、三氟乙酸、甲基磺酸,二茂铁甲酸等)分别与苯卟啉氢氧化锡反应,合成了21种未见文献报道的二羧酸苯卟啉锡:二(甲基磺酸)5,10,15,20-四(4-氯苯基)卟啉锡(A_4)、二(甲氧基乙酸)5,10,15,20-四(4-氯苯基)卟啉锡(A_5)、二(三氟乙酸)5,10,15,20-四(4-氯苯基)卟啉锡(A_6)等。通过元素分析、红外光谱、磁共振氢谱、单晶X-射线衍射等手段对结构进行了表征。并且解析了九个卟啉锡化合物的晶体结构;探讨了卟啉锡化合物在晶体中分子间的相互作用,分子间通过C-H×××O氢键及C-H×××π作用形成一维链状、二维网状超分子结构。紫外光谱表明,卟啉化合物与锡结合后Soret带发生了红移,锡原子上的氯被取代后,Soret带发生了蓝移。荧光光谱显示,卟啉锡化合物的激发波长在430nm处,它的最大发射波长与卟啉化合物相比发生了蓝移,卟啉锡有静态淬灭现象。电化学性质测试表明,二茂铁羧酸苯卟啉锡具有三个氧化峰,其他的卟啉锡化合物只有一个氧化峰。在二氯甲烷中,苯甲醛、对氟苯甲醛分别与吡咯在甲基磺酸催化下缩合,DDQ氧化,制得了2种N-错位卟啉化合物:5,10,15,20-四(4-氟苯基)N-错位卟啉(B_1)、5,10,15,20-四(4-苯基)N-错位卟啉(B_9)。在合成的N-错位卟啉化合物的错位N上进行烷基化,合成了8种未见文献报道的N-取代错位卟啉:2-N-乙氧羰基甲基-5,10,15,20-四(4-氟苯基)N-错位卟啉(B_2)、2-N-羧甲基-5,10,15,20-四(4-氟苯基)N-错位卟啉(B_3)、2-N-环戊氧羰基甲基-5,10,15,20-四(4-氟苯基)N-错位卟啉(B_4)等。利用元素分析、红外光谱、磁共振氢谱、单晶X-射线衍射等手段对结构进行了确认。解析了两个N-错位卟啉化合物化合物的晶体结构;研究了N-错位卟啉的荧光、紫外吸收等光物理性质。结果表明,N-错位卟啉的激发波长在420nm附近,当N-错位卟啉与金属离子发生配位时,其最大发射波长发生红移。本文探究了多种金属卟啉锡和N-错位卟啉的合成、结构以及性质,拓展了卟啉化学的研究内容,丰富了卟啉化合物的结构数据,为进一步研究其性质及应用提供了实验依据。
[Abstract]:Porphyrin and metalloporphyrin have been one of the hot spots in organic synthesis. The tin atoms of metalloporphyrin tin can combine with many kinds of electrophilic groups through oxygen atoms to form various kinds of axial coordination porphyrin compounds. It has been widely used as biomedical drugs, catalysts and nanomaterials. In this paper, 21 kinds of substituted phenylporphyrin tin and 10 N- dislocated benzene porphyrin compounds were designed and synthesized. Their structures were characterized by IR, NMR, elemental analysis, single crystal X-ray diffraction and so on. Their structural self-assembly, UV-vis absorption spectra, fluorescence spectra and electrochemical properties were also studied. A series of self-made 5-tetra (4-chlorophenyl) porphyrin compounds (A _ 1) and 5 ~ (10) (10) (4-methoxyphenyl) porphyrin (A _ (11),) porphyrins were prepared. The corresponding stannous porphyrin chloride was synthesized by the reaction of A21 porphyrin compounds with stannous chloride. After hydrolysis, stannous hydroxide of benzene porphyrin was obtained. Different organic acids (salicylic acid, trifluoroacetic acid, methyl sulfonic acid, ferrocene-formic acid, etc.) reacted with stannous hydroxide of benzene porphyrin, Twenty-one kinds of dicarboxylic acid phenylporphyrin tin: BIS (methyl sulfonic acid) 5 (methanesulfonic acid) 5 (4 chlorophenyl) porphyrin tin (A4), bis (methoxyacetic acid) 5 (methoxy acetic acid) 5 (10151520) tetra (4 chlorophenyl) porphyrin tin (A5) were synthesized. Bis (trifluoroacetic acid) 5-10 10 0-20-tetra (4-chlorophenyl) porphyrin tin (As 6), et al. The structure was characterized by elemental analysis, infrared spectroscopy, magnetic resonance hydrogen spectroscopy and single crystal X-ray diffraction. The crystal structure of nine porphyrin tin compounds was analyzed, and the intermolecular interaction of porphyrin tin compounds in the crystal was discussed. The molecular structure was formed by the interaction of C-H 脳脳脳 O hydrogen bond and C-H 脳脳脳蟺 in one-dimensional chain and two-dimensional reticular supramolecular structure. UV spectra showed that the Soret band of porphyrin compounds combined with tin shifted red and the Soret band of tin atoms was replaced by chlorine. The fluorescence spectra show that the excitation wavelength of the porphyrin tin compounds is at 430nm, and its maximum emission wavelength is blue shift compared with the porphyrin compounds, and the phenomenon of static quenching of porphyrin tin is observed. The electrochemical properties showed that there were three oxidation peaks in phenylporphyrin tin ferrocene carboxylate and only one oxidation peak in other porphyrin tin compounds. In dichloromethane, benzaldehyde, p-fluorobenzaldehyde and pyrrole were condensed with pyrrole in the presence of methyl sulfonic acid, respectively. Two N-dislocation porphyrin compounds were synthesized by DDQ oxidation. B _ S _ 9 _ (10 ~ 10) ~ (15) -Tetra (4-phenyl) N ~ (-) -dislocation porphyrin (B _ S _ 9). The alkylation of N on the synthesized N-dislocation porphyrin compounds was carried out. Eight kinds of N-substituted dislocation porphyrins, 2-N-ethoxycarbonyl-methyl-5, 10-151520-tetra (4-fluorophenyl) N-dislocation porphyrin (BSP), have been synthesized. 2-N- carboxymethyl-5 (1015) -tetra (4-fluorophenyl) N-dislocation porphyrin (B3), 2-N- cyclopentyloxycarbonyl methyl-5 (101520- tetra (4-fluorophenyl) N- dislocation porphyrin (B4) and so on. The structure was confirmed by elemental analysis, infrared spectroscopy, magnetic resonance hydrogen spectroscopy and single crystal X-ray diffraction. The crystal structure of two N-dislocation porphyrin compounds and their photophysical properties such as fluorescence and UV absorption were studied. The results show that the excitation wavelength of N- dislocation porphyrin is near 420nm, and the maximum emission wavelength of N- dislocation porphyrin is red-shifted when it is coordinated with metal ions. In this paper, the synthesis, structure and properties of various kinds of metalloporphyrin tin and N-dislocation porphyrin have been studied, the research contents of porphyrin chemistry have been expanded, the structure data of porphyrin compounds have been enriched, and the experimental basis has been provided for the further study of their properties and applications.
【学位授予单位】：曲阜师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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