Synthesis, Characterization And Performances Of Sulfur-containing Porphyrazines Used In Environmental Photocatalysis

Tetraazaporphyrin, or porphyrazine （Pz） and their derivatives, which have tightly fusedmacrocyclic structure and delocalized π-conjugate electron system, can mimetic oxidaseenzyme activate dioxygen degrade the organic pollutants in water under the mild condition,providing a green and efficient biomimetic photocatalytic method. to solve the organicpollutants in aquatic environment.To further improve the outer structure of the macrocyclic to enhance their π-conjugateelectron system and physical chemistry properties. so that the tetraazaporphyrin compoundsof this type performe excellent photocatalysis properties in degrade the organic pollutants. Wecombined the external soft electron-rich atoms（S, Se） and double bond to the perpheralmacrocycles enhance their physical chemistry properties. And investigated the self-assemblyof the tetraazaporphyrin with double bond in the perpheral macrocycles, The process withoutusing any template but covalently linked, and We get the ordered morphology of Pznanospheres.The specific research contents of this paper can be summarized in the following aspects:1．The tetrahydroxymethyl-tetra（1,4-dithiin）-porphyrazine CoPz（HO-CH₂-dtn）₄have beensynthesized according to the template method using2,3-dicyano-5-hydroxymethyl-1,4-dithiin as start material. And characterized by IR、UV-vis、¹H-NMR、¹³C-NMR、MS etc. Investigated the affection of the axial ligands to its photocatalytic activity. Provedthe exist of the·OH, O2,1O2in the photochemical process. Combine with the Uv-Vis andHPLC and MS，we can give the possible degradation mechanism of the degradationprocess.2. Synthesized the [2,3,7,8,12,¹³,17,18-Octakis（alkenylthio）phyrazinato]zinc（II）, Zn （OASPz）.And characterized by IR、UV-vis、¹H-NMR、¹³C-NMR、MS etc. Then conducted it toself-assembly, the morphology of the resulting nanosphere were investigated, TEMand SEM show the diameter distributions is between200to300nm.3. A asymmetry Pz tir （1,4-dithin）-（1,2,5） selenodiazolo-Pz and their metal complex hasbeen synthesized according to the template method by using2,3-dicyano-5-hydroxymethyl-1,4-dithiin and （1,2,5） selenodiazolo. And characterized by IR、UV-vis、¹H-NMR、¹³C-NMR、MS etc. And lay the foundation for the preparation of porphyrazine,sderivatives after dislodge of the selenium.