Synthesis,Characterization And Properties Of Tetra-carboxyl Tetra(1,4-dithiin) Porphyrazine

Using clean solar light and oxygen in air in the presence of photocatalysts to degrade organic pollutants in water is a very active research area at present. Degradation of environmental pollutants making the best of solar light is one of the effective ways for easing the increasingly aggravated environment pollution.Tetra-(1,4-dithiin)-porphyrazine which has the extended delocalized 18π-electrons of conjugated macrocyclic system. The results from the present investigation suggest that it has excellent photocatalytic properties. In order to improve the catalytic capability and hydrophilic of the porphyrazine, we succeeded in introducing electron-withdrawing carboxyl group at its periphery and prepared metal tetra-carboxyl(1,4-dithiin) porphyrazine (MPz(dtn-COOH)4) The photo reactivity of ZnPz(dtn-COOH)4 was studied through degrading dye pollutant Rhodamine B. In recent years, there have been some articles reported that porphyrins can be assemble to nanostructures and nanodevices, which showed not only their inherent photosensitive and photocatalytic properties but also their characteristic property of nanostructure and molecular assembly. Therefore, we aslo preliminary research the self-assembly properties of MPz(dtn-COOH)4 through the driving forces such as hydrogen-bonding, electrostatic interaction and stacking characterization. The main results are summarized as follow:1. Three novel tetra-carboxyl(1,4-dithiin)porphyrazine MPz(dtn-COOH)4 (M = Mg, H and Zn) have been synthesized by hydrolyzing the magnesium-tetra-ester (1,4-dithiin) propyrazine under alkaline conditions and template method. They are characterized by UV-vis, FT-IR and XPS.2. Rhodamine B as the model molecular of degradation, When the ZnPz(dtn-COOH)4 was loaded on the ion-exchange resin (Amberlite CG400) to activate oxygen for oxidative degradation of organic compounds, its photoreactivity of ZnPz(dtn-COOH)4 is estimated.3. By means of the flurescence techniques, we tested activate free radical in the catalyst system. Combining with UV-Vis and HPLC methods, we proposed a rough mechanism of degradation of RhB in pH = 3 aqueous solution.4. Study on self-assembly properties of MPz(dtn-COOH)4 with CTAB, DDAB and TMPyP in different pH conditions. MgPz(dtn-COO?·CTA+)4 has a good solubility; The UV-Vis, fluorescence spectroscopy and TEM images showed thatMPz(dtn-COOH)4 assembles with DDAB and TMPyP to get different morphology of nano and micron level and the solutions pH value have a significant impact on their morphologys.