Synthesis And Properties Of Tetra-Methyl-Tetra-(1,4-dithiin)- Transition-Metallo-Porphyrazines

The global attention to water pollution has become a key task in recent years. Biomimetic photocatalysis differs from other water treatment processes. It has extensive worthiness of research and applicable prospects for degrading toxic organic pollutants in the wastewater by mimicking the oxidative characteristics of iron-containing oxygenase enzymes under mild conditions.Iron(II)-tetra-(1,4-dithiin)-porphyrazine (abbreviated as FePz(dtn)4 ), which has an extended delocalized 18Ï€-electron conjugated macrocyclic system, shows excellent photoreactivity. FePz(dtn)4 can activate H2O2 and/or O2 to degrade the organic pollutants. Methyl, a electron-donating group, was sucessfully introduced onto tetra-(1,4-dithiin)-porph- yrazine to improve the lipophilic capability. The photoreactivity of metal-tetra-methyl-tetra -(1,4-dithiin)-porphyrazine (MPz(Me-dtn)4, M=Fe,Mn) were evaluated using RhB as a target molecule. The thesis mainly consists of three sections as follows:Section 1. MPz(Me-dtn)4 have been synthesized according to the template method from the prepared intermediate of 2,3-dicyano-5-methyl-1,4-dithiin.Section 2. We have investigated the physical properties of the MPz(Me-dtn)4 and the effect of central metal on the physical properties. Through introducing methyl groups, the lipophilic capability of porphyrazine have been greatly improved, and MPz(Me-dtn)4 show differently photophysical capability.Section 3. The photoreactivity of MPz(Me-dtn)4 are estimated through degrading Rhodamine B (RhB) under mild conditions. The aggregation shows lower reactivity than monomer, and the capability of activating molecular oxygen of FePz(Me-dtn)4 is much higher than MnPz(Me-dtn)4.