Substituted Benzene Synthesis, Characterization And Properties Of Porphyrin Compound

Porphyrin and metalloporphyrin derivatives have special conjugate structure and biologicalfunction. Substituents on the porphyrin ring will chang the compound nature. In this paper, somenew types of porphyrins and metalloporphyrin derivatives are designed and synthetized. Thestructures of these compounds are determined by IR,1H NMR, and elemental analysis. Thecrystal structures of the representative compounds are analyzed by the X-ray diffraction method.Their UV-Vis absorption, fluorescence spectrum, electrochemical property and inhibitory effecton E.coli are preliminary studied.1. Some new porphyrin compounds, such as tetra （3,5-dimethoxy-4-hydroxyphenyl）porphyrin （A₂）, tetra（3,5-dimethyl-4-benzyloxyl）porphyrin （A₃）, tetra（3,5-dimethoxy-4-benzyloxyl）porphyrin （A₄）,[tetra（3,5-dimethoxy-4-hydroxyphenyl）porphyrinato]zinc（A₅）,[tetra（3,5-dimethyl-4-benzyloxyl）porphyrinato]zinc（A₆）, are synthetized by using the A_dler-Longo methodand characterized by IR,1H NMR spectra. The crystal structures of A₂and A₃are analyzed by theX-ray diffraction method. The analyses of UV-visible spectra, fluorescence spectrum andelectrochemical property of the compounds show that substituent groups have an importantinflunce on the nature of the porphyrins. When there are electron-donors on the benzene rings,UV-visible absorption, fluorescence emission shift to the direction of the long wavelength andoccur red shift; when there are electron-withdrawing groups, UV-visible absorption, fluorescenceemission shift to the direction of the short wavelength and occur blue shift. The reasons are thatthey mainly related with the electron density of the porphyrin conjugate ring. When the electrondensity in the porphyrin rings increases, the electronic transition energy levels lower. Theabsorption and fluorescence emission occur the red shift. While the electron density decreases,electronic transition energy levels lift and the blue shift occur.2. A series of asymmetric porphyrin compounds were synthesized. The crystal structures of[5-（4-nitrophenyl）-10,15,20-triphenylporphyrinato]zinc （B₈） and [5-（4-methoxycarbonylphenyl）-10,15,20–triphenylporphyrinato]zinc （B₉） are analyzed by the X-ray diffraction. The resultsshow that they are both five-coordinated and possess distorted square pyramid. In compound B₈,the oxygen atom of methanol coordinates to zinc, and one-dimensional chain supramolecularstructure was formed through intermolecular weak interactions. While in compound B₉carbonyloxygen of ester coordinates to zinc of adjacent molecule and form one-dimensional chainpolymer.3. The fluorescence emission and antibacterial activity of compounds tetra （3,5-dimethoxy-4-hydroxyphenyl） porphyrin （A₂）,[tetra （3,5-dimethoxy-4-hydroxyphenyl） porphyrinato]zinc（A₅）,5-（4-methoxycarbonylphenyl）-10,15,20–triphenylporphyrin （B₆）, and [5-（4-methoxycar bonylphenyl）-10,15,20–triphenylporphyrinato]zinc （B₉） are determinated. The Q bands of A₅andB₉become two bands from four bands of the porphyrin ligands （A₂and B₆）. The mainly resionsare that the zinc ions increase symmetry of the porphyrin molecules and molecular orbitaldegeneracy and reduce the molecular orbital split. A₂, A₅, B₆, B₉have antibacterial activityagainst colibacillus and the minimum inhibiting concentrations are16.78,12.96,27.24, and23.08μg/ml,respectively. The introduction of metal ions enhances the antibacterial activity ofporphyrin derivatives.