Synthesis And Spectrum Properties Of Tetra-substituted Phthalocyanines

Phthalocyanines,with high thermal stabilities and chemical stabilities, display peculiar photo-electrical,thermal and magnetic characters。The structure of phthalocyanine molecule can be modified with metals and substitutes to obtain the required physical and chemical properties. Based on this, twenty new phthalocyanines with different substitutes on Pc ring and metals in the center of Pc were synthesized in this paper through solid phase and liquid phase methods. These compounds were characterized and the properties of them was studied.Synthesis and characterization: 1. The metal-free phthalocyanines and metallophthalocyanines with schiff basic were synthesized by liquid phase method. First,two precursors of the phthalocyanines were obtained by nucleophilic reactions, the precursors are 4-(2-Amlnothlophenol and 4-Hydroxybenzaldehydethio)phthalonitrile, 3-(2-Amlnothlophenol and 4-Hydroxybenzaldehydethio)phthalonitrile. Then two series of substituted phthalocyanines (8 kinds) were synthesized through"DBU method": tetra-β-(2-Amlnothlophenol and 4-Hydroxybenzaldehydethio)metal-free phthalocyanines,tetra-β-(2-Amlnothlophenol and 4-Hydroxybenzaldehydethio)metallophthalocyanines ,tetra-α-(2-Amlnothlophenol and 4-Hydroxybenzaldehydethio)metal-free phthalocyanines,tetra-α-(2-Amlnothlophenol and 4-Hydroxybenzaldehydethio)metallophthalocyanines. And they were characterized by Elemental Analysis, IR, 1H NMR and mass spectrum. 2. Twelve tetra-β-naphthalimidesmetallophthalocyanine were synthesized by tetraamide-phthalocyanine and 4-Br-1, 8-naphthalic anhydride, 4-hexahydropyridine-1,8-naphthalic anhydride, 4-morpholine-1,8-naphthalic anhydride through solid phase method. They are tetra-β-(4-Br-1,8-naphthalimides)metllophthalocyanine, tetra-β-(4-hexahydropyridine-1, 8-naphthalimides)metllophthalocyanine,tetra-β-(4-morpholine-1, 8-naphthalimides) metllo- phthalocyanine. The metal are Co(II),Ni(II),Cu(II),Zn(II), They were characterized by Elemental Analysis, 1H NMR, IR,UV-Vis spectra and mass spectrum. So far the two precursors and the twenty phthalocyanines had not been reported.Study on properties: The UV-Vis spectra of the two kinds Pc compounds were investigated in this dissertation. The effects of the structure including substituted group (kind and position), center metal and environment factor including acid,base and solution were discussed. The results indicate that theλmax in Q-band of the phthalocyanines we synthesized shift to red region with various degrees in contrast to the correspond non-substituted phthalocyanines and the absorption is narrower obviously. The blue shift order of theλmax in Q-band was Co(II) >Ni(II) >Cu(II) >Zn(II) with the increas e of metal polarization ability.The effects of substituted groups'position on the phthalocyanines'λmax in Q-band were much more distinct. Theλmax in Q-band ofαsubstitutedphthalocyanines red-shift extent was much more great than theβsubstituted phthalocyanines. The volume of substituted groups on the metallophthalocyanines still have some effects on theλmax in Q-band. The effects of acid and base on metallophthalocyanine was investigated in DMF. The acid and base have little affect to the schiff base but not to the naphthalimides phthalocyanine, the naphthalimides phthalocyanine was quickly decompounded to tetraamidephthalocyanine and their UV-vis spectra were converted to the UV-vis spectra of tetraamide-phthalocyanine in the base. The two kinds Pcs exhibit large change in different orgnic solvent, especially to theλmax in Q-band, the intensity of monomer and aggregation of naphthalimides phthalocyanines. These show that the affect of the solvent on the two kinds Pcs is strong.