【摘要】：卟啉以及金屬卟啉,一直是有機(jī)合成的熱點(diǎn)之一。金屬卟啉錫的錫原子通過(guò)氧原子可與多種親電基團(tuán)結(jié)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(xué)藥物、催化劑以及納米材料。本文主要設(shè)計(jì)合成了21種取代苯卟啉錫和10種N-錯(cuò)位苯卟啉化合物,通過(guò)紅外光譜、核磁共振氫譜、元素分析、單晶X-射線衍射等技術(shù)表征了其結(jié)構(gòu),并初步研究了它們的結(jié)構(gòu)自組裝、紫外-可見(jiàn)吸收光譜、熒光光譜、電化學(xué)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(yīng),合成了相應(yīng)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(jī)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(yīng),合成了21種未見(jiàn)文獻(xiàn)報(bào)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(guò)元素分析、紅外光譜、磁共振氫譜、單晶X-射線衍射等手段對(duì)結(jié)構(gòu)進(jìn)行了表征。并且解析了九個(gè)卟啉錫化合物的晶體結(jié)構(gòu);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(guò)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(jié)構(gòu)。紫外光譜表明,卟啉化合物與錫結(jié)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(lán)移。熒光光譜顯示,卟啉錫化合物的激發(fā)波長(zhǎng)在430nm處,它的最大發(fā)射波長(zhǎng)與卟啉化合物相比發(fā)生了藍(lán)移,卟啉錫有靜態(tài)淬滅現(xiàn)象。電化學(xué)性質(zhì)測(cè)試表明,二茂鐵羧酸苯卟啉錫具有三個(gè)氧化峰,其他的卟啉錫化合物只有一個(gè)氧化峰。在二氯甲烷中,苯甲醛、對(duì)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(cuò)位卟啉化合物:5,10,15,20-四(4-氟苯基)N-錯(cuò)位卟啉(B_1)、5,10,15,20-四(4-苯基)N-錯(cuò)位卟啉(B_9)。在合成的N-錯(cuò)位卟啉化合物的錯(cuò)位N上進(jìn)行烷基化,合成了8種未見(jiàn)文獻(xiàn)報(bào)道的N-取代錯(cuò)位卟啉:2-N-乙氧羰基甲基-5,10,15,20-四(4-氟苯基)N-錯(cuò)位卟啉(B_2)、2-N-羧甲基-5,10,15,20-四(4-氟苯基)N-錯(cuò)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(cuò)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(duì)結(jié)構(gòu)進(jìn)行了確認(rèn)。解析了兩個(gè)N-錯(cuò)位卟啉化合物化合物的晶體結(jié)構(gòu);研究了N-錯(cuò)位卟啉的熒光、紫外吸收等光物理性質(zhì)。結(jié)果表明,N-錯(cuò)位卟啉的激發(fā)波長(zhǎng)在420nm附近,當(dāng)N-錯(cuò)位卟啉與金屬離子發(fā)生配位時(shí),其最大發(fā)射波長(zhǎng)發(fā)生紅移。本文探究了多種金屬卟啉錫和N-錯(cuò)位卟啉的合成、結(jié)構(gòu)以及性質(zhì),拓展了卟啉化學(xué)的研究?jī)?nèi)容,豐富了卟啉化合物的結(jié)構(gòu)數(shù)據(jù),為進(jìn)一步研究其性質(zhì)及應(yīng)用提供了實(shí)驗(yàn)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(xué)位授予單位】：曲阜師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O641.4

【參考文獻(xiàn)】

相關(guān)期刊論文 前10條

1 王濤;郝曉玲;常旭;韓士田;劉彥欽;;卟啉分光光度法測(cè)定豆類微量Cu(Ⅱ)含量[J];中國(guó)糧油學(xué)報(bào);2009年10期

2 蓋秀蘭;劉軍;;摻雜卟啉凝膠膜熒光分析法測(cè)定鋅鎘汞[J];淮陰師范學(xué)院學(xué)報(bào)(自然科學(xué)版);2009年02期

3 麻明友;熊利芝;肖卓炳;;鐠卟啉的固相合成與表征[J];吉首大學(xué)學(xué)報(bào)(自然科學(xué)版);2009年03期

4 詹海鶯;劉海洋;胡軍;江煥峰;;卟啉超分子的組裝合成及其應(yīng)用新進(jìn)展[J];中國(guó)科學(xué)(B輯:化學(xué));2009年03期

5 周連文;;meso-四(4-吡啶)卟啉分光光度法測(cè)定蔬菜中微量銅[J];食品科技;2008年12期

6 曾卓;廖子英;唐天聲;陳超森;;含氟卟啉的研究進(jìn)展[J];有機(jī)化學(xué);2007年01期

7 丁玉龍,李賀,杜斌,魏琴,段彩虹;卟啉試劑合成的研究進(jìn)展[J];濟(jì)南大學(xué)學(xué)報(bào)(自然科學(xué)版);2005年03期

8 謝瓊玉,趙鴻斌,王霞瑜,羅和安,齊紅蕊,彭圣明,顧崢;meso-四(對(duì)烷氧基苯基)卟啉配合物的合成、表征和液晶性研究[J];無(wú)機(jī)化學(xué)學(xué)報(bào);2004年11期

9 唐波,馬驪,王洪鑒;新型主體化合物在生物活性分子分析中的應(yīng)用新進(jìn)展[J];分析化學(xué);2002年04期

10 趙鴻斌,蔡劍,林原斌,劉鍵,羅志強(qiáng),寧?kù)o恒,周盡花;四(對(duì)烷氧苯基)卟啉及其金屬絡(luò)合物的光譜分析[J];分析化學(xué);2000年04期

，

本文編號(hào)：2319531