Synthesis, Separation And Characterization Of Low Symmetrical Sulfur-containing Metal-porphyrazine

The two cornerstones in tetrapyrrolic macrocycle systems are porphyrins and tetraazaporphyrins (also called as porphyrazines), which include phthalocyanines. As porphyrins and phthalocyanines, porphyrazines have a closely fused macrocyclic skeleton with an extendedly, delocalizedly conjugated macrocyclicπ-system and high stabilities for heat and light, acid-resistance, base-resistance and excellent performance of electron etc., and having more and more attracted considerable attention from scientists of many fields. Especially, metal-porphyrazines now display an extensively applicable prospects for degrading toxic organic pollutants in the wastewater by mimicking the oxidative characteristics of iron-containing oxygenase enzymes under mild conditions.According to the principle of crystallography, Unsymmetrical substance often represents some especial properties. Many literatures reported that the catalytic activity of unsymmetrical and low symmetrical molecules was better than the one of symmetrical. We synthesized the low symmetrical metalloporphyrazines from prepared intermediate of 2,3-dithiolate-1,4-dithiin, 1,3-diiminoisoindoline, 4-nitrophthalic nitrile and 4-pentyloxy- phthalic nitrile, based on having realized the synthesis of tetra(1,4-dithiin) tetra-pophyrazine (FePz(dtn)4). We successfully also separated the 1,4-dithiin-4-pentyloxy phenyl-porphyrazine, a novel and diffluent complex, by column chromatogram.The thesis mainly consists of four sections as follows:1. Progress on phthalocyannie, porphyrazines and dissymmetrical porphyrazines was introduced. Their synthesis routes, separating methods and prospects of the application were systemally reviewed. Herein, the idea and sinification for studying on the topic were also raised.2. The first low symmetrical metalloporphyrazines, iron(II) di(1,4-dithiin) diphenyl- porphyrazine, was synthesized by the template method using 2,3-dithiolate-1,4-dithiin and 1,3-diimino-isoindoline (logogram: FePcPz(dtn)n) as precursors. Then the product was modified by chloridizing for improving disolubilitiy and analyzed for the type of the composition by HPLC.3. The second low symmetrical porphyrazines, iron(II) di(1,4-dithiin)-di(4-nitrylphenyl) porphyrazine, was synthesized by the template method using 2,3-dithiolate-1,4-dithiin and 4-Nitrophthalonitrile (logogram: FePc(NO2)nPz(dtn)n) as precursors. The above compound was characterized by UV-vis, FT-IR, etc. Then the compound was separated by semi-preparative HPLC.4. A novel and soluble low symmetrical porphyrazine, magnisum or iron tri(1,4-dithiin)- (4- pentyloxy-phenyl) porphyrazine, was introduced. Based on the experience of synthesizing the above two compounds, we first displaced the nitryl of the 4-nitrophthalic nitrile by a large group—pentyloxy to form the precursor 4-pentyloxy phthalic nitrile. Then the 4-pentyloxy-phthalic nitrile react with 2,3-dinitrile-1,4-dithiin in a large amount-of-reactant ratio (1:10 mol/mol) in the Mg(OC4H9)2 solvent. The single object product was gained by using the column chromatograph filled with silica gel and characterized by UV-vis, FT-IR, 1HNMR and EA. Finally, the solubility and catalyse capability of the complex was explored roughly.