Synthesis And Properties Studies On Unsymmetrical Amido Porphyrins And Their Compounds

The porphyrins, served as one kind of macrocyclic compounds, have a great variety of types and different structures, and they are important in the field of biochemistry owing to their various biological properties. As the particular structure and the nature of the porphyrins, they have potential applied background in the field of photo–electronic conversion, bionics, photodynamic therapy, optoelectronic devices, sensors, molecular logic devices, catalytic materials, information storage materials, solar storage, molecular recognization, etc. So that multitudinous chemists and biochemists all over the world did well research in the areas of syntheses, structures, functions and properties of the porphyrins.The first liquid crystalline porphyrin derivative was reported by Goodby et al. in 1980. Since then, many mesogenic porphyrins have been synthesized and their mesomorphicproperties were investigated. But up to now, most of the side chains of TPP derivative liquid crystals are alkyl, alkoxy, or acyloxy group, those bearing the alkylamido group as side chains porphyrin liquid crystals have been reported little. Whether the alkylamidophenylporphyrins show liquid crystal properties or not and what kind of liquid crystals they are asise our interest. So a series of unsymmetrical amidophenylporphyrin ligands and their metal complexes were synthesized and their liquid crystal properties were studied.The preparation of well defined arrays of porphyrins is a popular area of research,for oligomeric porphyrins with an attractive prospect in light, electricity, magnetism domains, play a number of critical biological roles such as energy and electron transfers,molecular binding,multielectron redox catalysis,light harvesting, and in organic magnetic materials. The study of metalloporphyrin oligomers came of the research on natural porphyrin polymers. Metalloporphyrin oligomers as important compositions of chlorophyll reaction active center in photosynthesis reaction courses of the green plants and bacterial play a crucial role in charge-transfer and charge-separation and important biological effect. In order to search special porphyrin, it is important for us to mimic the structure and function of natural porphyrin oligomers.In this paper, nine unsymmetrical amidophenylporphyrin ligands and their twelve transition metal complexes were synthesized and characterized by means of elemental analysis, MS, UV-Vis, IR and 1H NMR. Furthermore, we have investigated these compounds by Resonance Raman spectra, cyclic voltammetry, thermal studies and fluorescence spectroscopy. These studies will provide wider ground for choice and application of the materials. Our work includes the following aspects:1. Three unsymmetrical amidophenylporphyrin ligands and their six transition-metal complexes were synthesized. All of them have been characterized, assigned and analyzed by elemental analysis, MS, UV-Vis, IR and 1H NMR. The electrochemical, photochemical, photophysical and thermal properties of the compounds have been analyzed by cyclic voltammetry, Raman spectra and fluorescence spectra. The effects of chain length on their properties have also been studied.2. Three unsymmetrical pyridineamidophenylporphyrin ligands and their zinc complexes were synthesized. All of them have been characterized, assigned and analyzed by elemental analysis, MS, UV-Vis, IR and 1H NMR. Properties of the compounds have been analyzed by cyclic voltammetry, Raman spectra, fluorescence spectra and TG/DTA. The effects of their properties have also been studied. 3. An unsymmetrical pyrazinoicamidophenylporphyrin ligand and its zinc complexe were synthesized. All of them have been characterized, assigned and analyzed by elemental analysis, MS, UV-Vis, IR and 1H NMR. Properties of the compounds have been analyzed by cyclic voltammetry, Raman spectra, fluorescence spectra and TG/DTA. The effects of their properties have also been studied. 4. Two unsymmetrical porphyrin ligands of succinylamidophenylporphyrin and maleilacylamidophenylporphyrin and their zine complexes were synthesized. All of them have been characterized, assigned and analyzed by elemental analysis, MS, UV-Vis, IR and 1H NMR. Properties of the compounds have been analyzed by cyclic voltammetry, Raman spectra, fluorescence spectra and TG/DTA. The effects of their properties have also been studied.