Syntheses And Properties Of Tetra-substituted Metal Phthalocyanines

Phthalocyanine is a kind of microcycle compound with well thermal stabilities and chemical stabilities. In recent years, many special characters and novel functions have been found, The field of applications will increase widely .they can be used in many fields ,such as Secondary Battery, electrochromic substances ,chemistry sensors ,solar energy cells, laser recorder materials ,nonlinear optics , magnetism materials ,catalysis and so on. the interrelated basic investigations and application investigations are widely focused attention upon. However, Phthalocyanine compounds can't be resolved easily which limites their application. So the structure of phthalocyanine molecule has to be modified to improve their solubilities and obtain the required physical and chemical properties. The effective method is importing functional groupe to center, circumference and axes of phthalocyanine compounds. Based on this, several metallophthalocyanines substituted with different types of azo-aromaticoxy in different position(α-position andβ-position) of the Pc ring were synthesized in this paper through"DBU method".These compounds were characterized and studied on properties.Synthesis and characterization: five precursors for the synthesis of metallophthalocyanines were obtained by nucleophilic reactions, the precursors are 4-(5-chlorine-8-quinolinoxy)phthalonitrile, 3-(5-Methoxyquinolin-8-quinolinoxy)phthalonitrile, 4-(5-Methoxyquinolin-8-quinolinoxy)phthalonitrile,4-(5-Ethoxyquinolin-8-quinolinoxy)phthalonitrile,4-(5-Propoxyquinolin-8-quinolinoxy)phthalonitrile. And they were characterized by Elemental Analysis, IR, 1H NMR. 2. Two series of substituted metallophthalocyanines (21 kinds) were synthesized through"DBU method": tetra-β-(5-chlorine-8-quinolinoxy)metallophthalocyanines,tetra-α-(5-Methoxyquinolin-8-quinolinoxy)metallophthalocyanines,tetra-β-(5-Methoxyquinolin-8-quinolinoxy)metallophthalocyanines,tetra-β-(5-Methoxyquinolin-8-quinolinoxy)metal-free phthalocyanines,tetra-β-(5-Ethoxyquinolin-8-quinolinoxy)metallophthalocyanines,tetra-β-(5-Propoxyquinolin-8-quinolinoxy)metallophthalocyanines. They were characterized by Elemental Analysis, IR,UV-Vis spectra and mass spectrum. So far 5 kinds of precursors and 21 kinds of metallophthalocyanines had not been reported.Study on properties: The UV-Vis spectra of title compounds were investigated in this dissertation.The effects of substituted group (kind and position), center metal onλmax in their Q-band were discussed. The results indicate that theλmax in Q-band of the metallophthalocyanines we synthesized shift to red region with various(5-26nm) degrees in contrast to the correspond non-substituted metallophthalocyanines. The absorptiometer is narrower than before obviously. The blue shift order of theλmax in Q-ba nd was Co(II) >Ni(II) >Cu(II) >Zn(II) with the increase of metal polarization ability.The effects of substituted groups'position on the metallophthalocyanines'λmax in Q-band were much more distinct. Theλmax in Q-band ofαsubstituted metallophthalocyanines shift to red region(15-20nm) was much more distinct thanβsubstituted metallophthalocyanines. The effects of the cubage of substituted groups on the metallophthalocyanines,λmax in Q-band were not distinct. Fluorescence spectrum of part metallophthalocyanines was investigated in DMF. The effects of center metal and substituted group were discussed at the same time. The results show that the complex tetra-β-(5-Methoxyquinolin-8-quinolinoxy) zinc phthalocyanines,tetra-β-(5-Methoxyquinolin-8-quinolinoxy) zinc phthalocyanines and tetra-β-(5-Propoxyquinolin-8-quinolinoxy)zinc phthalocyanines are all have strong fluorescence intensity. therefor, these compounds will possible have some applications in empoldering photosensitizers in photodynamic therapy and the research of fluorescence diagnostizers .