Synthesis And Studies Of Their Application As Functional Materials On (Alkylthio) Tetraazaporphyrine And Their Transition Metal Coordination Compounds

The two cornerstones in tetrapyrrolic macrocycle ring systems are porphyrins and tetraazaporphyrins, which include phthalocyanines and porphyrazines. Like porphyrins and phthalocyanines, porphyrazines has a two-dimensionally developed molecular skeleton with associated extensive electron delocalization and implied chromophoric properties, high thermal stability, sublimability, acid-resistant, base-resistant and excellent electronic properties etc., Owing to their peculiar physical properties and special structure, they have more and more attracted considerable attention in many fields. They are not only extensively used in the fields of dyes, pigments, but also have a potential attractive prospects in the field of molecular materials and apparatus, photoelectric storage and display, solar battery, catalyzer, photocatalysis and electrocatalysis, phototherapy i.e.Transition metallicporphyrazines peripherally substituted with thioether groups are a new interesting class of complexes. Among the (alkylthio)tetraazaporphyrins, the macrocycle systems is become more richer in electrons for the sulfer element with abundant electrons .The special structure gives their special application especially in the area of high technologies, such as in liquid crystals, Langmuir-Blodgett films, ion-selectivity molecular apparatus, catalyzer, photocatalysis and electrocatalysis, phototherapy,i.e. According to the symmetrical principle, lower symmetrical materials usually show some specific physical and chemical characteristic and distinguish quality. In this paper, concretely, we described the synthesis of the new (alkylthio)tetraazaporphyrins, 2,3,7,8,12,13-hexakis(methylthio) -17,18-mono(dithiin) porphyrazine, [H2Pz(dtn)(mt)6], and their transition metal complex MPz (dtn)(mt)6[M = Co, Cu, Zn] by the template reaction. The primary material are 2,3-dicyano-5, 6-dihydro-l,4-dithiin and 1,2-dicyano-1,2-bis(methylthio)ethylene which are prepared by the method of Bahr et al. The characterization of the compound was carried out by the methods such as Elemental Analyzer, Mass Spectrum, HNMR, IR spectra. Their electronic spectra in different solvents and emission and excited fluorescence specta in chlorobenzene were studied. And we also reported their optimization and theoretical results with quantum chemistry theory, which seven porphyrazines compounds were designed and optimized in semi-empirical PM3 method of SCF, and their IR spectra in air condition were calculated. The functional study of the porphyrazine which modifying on cathode material, uncrystallized type MnO2, was carried out in lithium ion battery.This paper is consists of five chapters.In the chapter one, we systematically gave the summary of the developing about phthalocyanine and porphyrazines in classes, syntheses routes, methods for separatingporphyrazines and the prospects in the application. Therein, we explained the reasons, signification methods for studying about the topics.In the chapter two, we described the synthesis and their apparatus for precursores of the porphyrazine by the method of the presented papers, such as the preparation of the methyl iodide, disodium dimercaptomaleonitrial (Na2mnt), l,2-dicyano-l,2-bis(methylthio) -ethylene, 2,3-dicyano-5,6-dihydro-l,4-dithiin. The transition metallicporphyrazine complex compounds of copper, zinc and cobalt were synthesized with two methods or three routes. We also discussed the process of purification about porphyrazines, such as column chromatogram accompanying with UV spectrum.In the chapter three, we characterized the above compounds by the methods such as Elemental Analyzer, Mass Spectrum, HNMR, IR, etc, and studied their electronic spectra in different solvents, emmision and excited fluorescence spectrum in chlorobenzene.In the chapter four, we designed six types of alkylthio porphyrazine molecular and one type of thiohydrogen porphyrazine molecular, H2Pz(mt)g, H2Pz(dtn)4, czs-H2Pz(dtn)2(mt)4, fnmy-H2Pz(dtn)2(mt)4, H2Pz(dtn)3(mt)2, H2Pz(dtn)(mt)6, H2Pz(SH)8, and gave their optimizing structure accor...