Synthesis And Properties Of A Series Of Metallporphyrin-Schiff Bases

The synthetic route was focused on the preparation of meso-tetra (4-aminophenyl) porphyrin (TAPP). After metallation, the related complexes were further condensed with substituted benzaldehyde to form the Schiff-base configuration. These peripheral modifications around porphyrin rings can obviously affect electron transfer in conjugated π obits and therefore, the UV-Vis determinations spectra revealed recorded their change for both shapes and positions. Meanwhile, the introduced side groups can simplify purification and separation of the target compounds. In these peripheral modifications, different aldehydes and ketones would be selected to linked the amino groups, as result, the complexes with metalloporphyrin centers with different configurations will exhibit much more functionalities.Herein12porphyrin-Schiff-base compounds were prepared based on meso-tetra (4-aminophenyl) porphyrin and its related complexes condensing with different substituted benzaldehydes. The typically substituted benzaldehydes, including benzaldehyde,4-nitrobenzaldehyde,4-formylbenzoic acid and4-methoxybenzaldehyde, were selected in Schiff-base’s condensations, and the prepared porphyrin-Schiff-bases were list as follows: meso-tatra (N-benzylidene-4-methylaniline) porphyrin and its znic and cobalt complexes, moso-tetra [4-methyl-N-(4-nitrobenzylidene)aniline] porphyrin and its znic and cobalt complexes, moso-tetra [4-carboxilicbenzyl-N-4-aniline] porphyrin and its znic and cobalt complexes, moso-tetra [4-methoxybenzyl-N-4-aniline] porphyrin and its znic and cobalt complexes.This thesis is divided into three chapters.In chapter1, the synthetic methods and development of porphyrin compounds were reviewed. Notably, the research on metalloporphyrin-Schiff-bases was intensively introduced. The recently reported works about molecular wire based on metalloporphyrin complexes have been summarized. In the end, the experimental design and research containing were proposed.In chapter2, the synthetic method, characterization and spectral properties of meso-tetra (4-aminophenyl) porpphyrin were discussed. At beginning, meso-tetra (4-nitrophenyl) porphyrin (TNPP) was prepared by Adler’s way, then it was reduced by SnCl2in acid medium to form meso-tetra (4-aminophenyl) porphyrin (TAPP), and several related complexes were synthesized by reflux of DMF solution with porphyrin and responding metal salts. All obtained compounds were characterized by determinations of UV-Vis, IR, FL5EPR and’H-NMR. The electron effect of peripherally substituted phenyls around porphyrin rings were discussed in detail.In chapter3,12porphyrin-Schiff bases were prepared by condensations of meso-tetra (4-aminophenyl) porphyrin (TAPP) with different substituted benzaldehydes. This purpose compounds were characterized by normal determinations, and their photoelectric properties were also examined by determinations of UV-Vis, IR, FL, EPR and1H-NMR. Determination results indicated that the change in spectral property, especially the changes in electron transfer energy of conjugated obits of (metallo)porphyrin molecules were primarily affected by the electron effects of the peripherally substituted phenyls, and several interesting conclusions were obtained according to determining results.