Synthesis And Optical Properties Of Metallic Phthalocyanines

Since the discovery of phthalocyanine,increasing research efforts have been devoted into the macro-cycle molecules containing 18-πelectrons.The phthalocyanine functional materials have been widely used in many aspects,including the fabrication of chemical sensors and photodynamic therapy,copper phthalocyanine for liquid crystal light valve and gas sensor,conductive polymer and catalysts derived from the linear conjugated nickel phthalocyanines,sulfonated cobalt phthalocyanine for removal of mercaptan oil accumulation etc.At present,researches on phthalocyanine are divided into two sections,variation of the central coordination metal ions and the peripheral structure.The changes of the outer ring structure expend the application of phthalocyanine functional materials,the modification of different peripheral substitutes of phthalocyanine ring can bring additional functionalities,and more physical and chemical properties are integrated to phthalocyanine at the same time.In short,phthalocyanine has been widely used as a new type of advanced material in many emerging and cutting-edge areas.In this thesis,a series of highly conjugated bisphthalonitrile precursors were synthesized,and the bisphthalonitrile were utilized to prepare the branched metallic phthalocyanine.The chemical structures,surface morphology and photophysical properties of synthesized zinc phthalocyanines for different reaction time and chemical structures were systematically studied.In addition,a kind of magnetic nanospheres was prepared by combing the branched metallic phthalocyanine with Fe₃O₄ nanoparticles.The composite nanospheres have excellent adsorption and photocatalytic properties towards organic dyes.Firstly,a series of metallic phthalocyanines with solid-state fluorescence emission have been synthesized via the one-step cyclo-addition reaction of a biphenyl phthalonitrile precursor.The copper phthalocyanines with desired optical properties have been selected to further study the relationship among reaction time,molecular weight and fluorescence properties.We found that the branched phthalocyanine with a reaction time of 4 h showed the optimal fluorescence emission characteristics at 365 nm UV excitation.In addition,the fluorescence properties of the phthalocyanine copper in the solution state are also obtained.We continue to introduce carboxyl and sulfonategroups on the outer ring structure,which contributed to the preparation of water soluble branched phthalocyanine.In order to further explore the photocatalytic performance of branched metallic phthalocyanine towards organic dye molecules,we have systematically studied the photospectroscopy evolution of organic dyes（rhodamine B and methylene blue）solution in the presence of metallic phthalocyanine photocatalysts.On the other hand,we also have introduced carboxyl groups into the branched phthalocyanine and evaluated the evolution of absorption,it was found that the introduction of carboxyl changed branched phthalocyanine microstructure has the better adsorption ability of organic small molecules.Finally,we prepared a kind of magnetic composites microspheres with a particle size around 300 nm by growth of metallic phthalocyanine on the surface of Fe₃O₄nanoparticles.It was found that the composited microspheres not only exhibit the photocatalytic capacity derived from metallic phthalocyanine,but also maintained the magnetic properties of core nanoparticles,which implied that the obtained magnetic microspheres can be used as the recyclable absorbent for organic dyes removal without generation of secondary pollution.