【摘要】：卟啉以及金屬卟啉,一直是有機合成的熱點之一。金屬卟啉錫的錫原子通過氧原子可與多種親電基團結合形成多種類型的軸向配位卟啉化合物。已被廣泛用作生物醫(yī)學藥物、催化劑以及納米材料。本文主要設計合成了21種取代苯卟啉錫和10種N-錯位苯卟啉化合物,通過紅外光譜、核磁共振氫譜、元素分析、單晶X-射線衍射等技術表征了其結構,并初步研究了它們的結構自組裝、紫外-可見吸收光譜、熒光光譜、電化學等性質(zhì)。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))卟啉化合物分別與氯化亞錫反應,合成了相應的苯卟啉氯化錫。水解后得到苯卟啉氫氧化錫。使用不同的有機酸(水楊酸、三氟乙酸、甲基磺酸,二茂鐵甲酸等)分別與苯卟啉氫氧化錫反應,合成了21種未見文獻報道的二羧酸苯卟啉錫:二(甲基磺酸)5,10,15,20-四(4-氯苯基)卟啉錫(A_4)、二(甲氧基乙酸)5,10,15,20-四(4-氯苯基)卟啉錫(A_5)、二(三氟乙酸)5,10,15,20-四(4-氯苯基)卟啉錫(A_6)等。通過元素分析、紅外光譜、磁共振氫譜、單晶X-射線衍射等手段對結構進行了表征。并且解析了九個卟啉錫化合物的晶體結構;探討了卟啉錫化合物在晶體中分子間的相互作用,分子間通過C-H×××O氫鍵及C-H×××π作用形成一維鏈狀、二維網(wǎng)狀超分子結構。紫外光譜表明,卟啉化合物與錫結合后Soret帶發(fā)生了紅移,錫原子上的氯被取代后,Soret帶發(fā)生了藍移。熒光光譜顯示,卟啉錫化合物的激發(fā)波長在430nm處,它的最大發(fā)射波長與卟啉化合物相比發(fā)生了藍移,卟啉錫有靜態(tài)淬滅現(xiàn)象。電化學性質(zhì)測試表明,二茂鐵羧酸苯卟啉錫具有三個氧化峰,其他的卟啉錫化合物只有一個氧化峰。在二氯甲烷中,苯甲醛、對氟苯甲醛分別與吡咯在甲基磺酸催化下縮合,DDQ氧化,制得了2種N-錯位卟啉化合物:5,10,15,20-四(4-氟苯基)N-錯位卟啉(B_1)、5,10,15,20-四(4-苯基)N-錯位卟啉(B_9)。在合成的N-錯位卟啉化合物的錯位N上進行烷基化,合成了8種未見文獻報道的N-取代錯位卟啉:2-N-乙氧羰基甲基-5,10,15,20-四(4-氟苯基)N-錯位卟啉(B_2)、2-N-羧甲基-5,10,15,20-四(4-氟苯基)N-錯位卟啉(B_3)、2-N-環(huán)戊氧羰基甲基-5,10,15,20-四(4-氟苯基)N-錯位卟啉(B_4)等。利用元素分析、紅外光譜、磁共振氫譜、單晶X-射線衍射等手段對結構進行了確認。解析了兩個N-錯位卟啉化合物化合物的晶體結構;研究了N-錯位卟啉的熒光、紫外吸收等光物理性質(zhì)。結果表明,N-錯位卟啉的激發(fā)波長在420nm附近,當N-錯位卟啉與金屬離子發(fā)生配位時,其最大發(fā)射波長發(fā)生紅移。本文探究了多種金屬卟啉錫和N-錯位卟啉的合成、結構以及性質(zhì),拓展了卟啉化學的研究內(nèi)容,豐富了卟啉化合物的結構數(shù)據(jù),為進一步研究其性質(zhì)及應用提供了實驗依據(jù)。
[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.
【學位授予單位】：曲阜師范大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O641.4

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