Synthesis, Photoelectric Properties And Self-assembly Behaviors Of Meta-substituted Porphyrin Derivatives

Porphyrin material has broad application in photoelectric fields for its large π-conjugated structures and a multitude of active groups, as well as strong π-π interactions. Metal-porphyrin compounds with well photophysical, photochemical, electrochemical and self-assembly properties can be used as novel functional materials by modified of molecular structures.In the paper, we synthesized a novel series of porphyrin derivatives containing different electron-donors and acceptors through2+2MacDonald and coupling reactions. This article focuses on the study of photoelectric, self-assembly and third-order nonlinear optical properties of porphyrin derivatives The main contents are as follows:1. A series of zinc porphyrins intermediates containing alkoxy phenyl groups were synthesized. The π-conjugated range and solubility were improved by the introduction of long alkoxy groups, as well as the processing properties. The π-conjugated structures of compounds were adjusted by introducing different electron-donors and acceptors; In addition, we creatively modified the porphyrin derivatives using2+2click chemistry which could reduce the difficulty of the material synthesis. The photoelectric properties of the compounds were characterization by UV-Visible and PL spectroscopy and the results indicated that these porphyrin derivatives could be well used as dye photo sensitizer and nonlinear optical materials. Besides, the photo-responsibilites of the compounds were obviously improved by modification through click chemistry.2. The third-order nonlinear optical properties of the porphyrin derivative were investigated by Z-scan techniques, as well as the influences of different substituents on the nonlinear optical parameters. Typical reverse saturable absorption-saturable absorption transitions were observed by modification through click chemistry and the results indicated that the third-order nonlinearities were depended on the size of π-conjugated ranges3. The photovoltaic properties of a series of D-π-A porphyrin derivatives were investigated by electrochemical measurements. Study on the influences of different substituents on the photovoltaic properties indicated that the electron-donors could affect the short circuit current of the porphyrin derivatves and the open circuit voltage was mainly dependent on the movement of conduction band of the dye molecules. Further we investigated the relations between the molecular electron structures and the photoelectric conversion efficiency of the porphyrin dyes which could help to the application of porphyrin in dye-sensitized solar cells.4. Hydrogen bonding. π-π interactions and metal coordination were introduced into the porphyrin molecules and the self-assembly properties of the porphyrin derivatives were investigated by solvent-exchange methods. The results indicated that by modification of click reactions, the porphyrin derivatves could well self-assembly into regular morphologies which could contribute to the improvements of third-order nonlinear optical properties and photovoltaic properties.