Study On Substituent Effects Of Near Infrared Luminescent Metallic Porphyrins

Metal-porphyrin complexes are widely used in biomimetic chemistry,material chemistry,biomedicine and organic photoelectric materials.This dissertation mainly focuses on the design and synthesis of various metal porphyrins,through the exploration of their structural characterization and optical properties,to deepen the understanding of the effect of substituent effect on the luminescence properties of metal porphyrin complexes.Part one:Study on the substituent effect of lanthanide metalloporphyrin complexes in near infrared luminescence.We have synthesized a series of lanthanide metalloporphyrin complexes with different structures by modifying the phenyl groups at the meso site of porphyrins.Crystals of F₂₀TPP were obtained for the first time.Through the investigation of the UV-Visible absorption spectrum and near-infrared fluorescence spectrum properties of the series of lanthanide metalloporphyrin complexes,we found that the electron cloud density of porphyrin were increased can promote the absorption redshift,enhance the near-infrared emission intensity,and prolong the luminescence lifetime.Part two:Optical properties of polyfluoroalkyl transition metal porphyrins.By using"Chen’s reagent"（FSO₂CF₂CO₂CH₃）,we have synthesized polyfluoroalkyl porphyrin（β-tetrafluoromethyl-porphyrin）and its metal complexes（M-（CF₃）₄-TPP）.By comparing the spectral properties of polyfluoroalkyl porphyrin and tetraphenyl porphyrin,we found that the UV-Visible absorption peaks showed a significant redshift after the trifluoromethyl was introduced at the position of porphyrins pyrrole.Moreover,the structures of polyfluoroalkyl transition metal porphyrins were identified,and the influence of solvent on the optical properties of these series of polyfluoroalkyl transition metal porphyrins were explored.The absorption peaks of polyfluoroalkyl copper porphyrin and polyfluoroalkyl zinc porphyrin were promoted redshift with the polarity increased of solvent,but it had slight effect on polyfluoroalkyl palladium porphyrins and polyfluoroalkyl nickel porphyrin.