Synthesis, Characterization And Property Research On Different Substituted Phthalocyanine Metal Compounds

The presented work focuses on the applied basic research on the substituted phthalocyanine metal compounds. The main work and results are summarized as following:1. Tetra-β-( potassium sulfonate)phthalocyanine zinc, mixture of β-(potassium sulfonate) phthalocyanine zinces, tetra-a-(2,2,4-tirmethyl-3-pentoxy) phthalocyanine metal compounds (M=Co, Ni, Cu, Zn, VO)and tetra-a-(2,4-di-tert-butylphenoxy) phthalocyanine vanadium-oxo were synthesized by template reaction of corresponding substituted (and unsubstituted) phthalonitril(s), using 1.8-diazabicyclo[5.4.0] undec-7-ene (DBU) or ammonium molybdate as catalyst. The mixture of sulfonated phthalocyanine zinc [ZnPcSn, S representing for P-(potassium sulfonate) group, n=0-4] was separated by high preferment liquid chromatogram (HPLC) to obtain the ZnPcS₁, ZnPcS₂ and ZnPcS₃ compositions, respectively. The distribution of different sulfonated compositions in the product was analyzed by HPLC to find out the effect of proportion of 4- (potassium sulfonate) phthalonitril /unsubstituted phthalonitril. The isomer composition of these ZnPc compositions and the phthalocyanine metal compounds with alkoxy or aryloxy substituents was analyzed by HPLC, too. All of these compounds were characterized and confirmed by elemental analyses, MS, IR. and UV-Vis spectroscopy.2. The aggregation of these well-defined (substituted position and number) sulfonated phthalocyanine zinc compositions was studied in water, phosphate-triethylamine buffer, KOH and dimethylsulfoxide solution. Their photocytotoxicity toward 3 tumor cell lines was investigated in vitro. The ZnPcS₂ composition was found to be the most effective one to all of the cell lines.3. UV-Vis spectra (specially the Q-band absorption), fluorescence spectra, time resolved absorption spectra under flash photolysis and the abilities of these compounds to photo-generating singlet oxygen (¹O₂) were investigated. The effect nature of center metal, kind and position of substituted group(s) on the properties of these photochemical and photophysical properties were discussed.4. The electrochemistry study of alkoxy and aryloxy substituted phthalocyanineswas carried out in DMF containing 0.1 M TBAP. The cyclic voltammetry and thin-layer UV-visible spectroelectrochemistry showed that they have similar properties of the corresponding unsubstituted ones. The LB film of tetra-a-(2,4-di-tert-butylphenoxy) phthalocyanine metal compounds (M=Co, Ni, Cu, VO) were prepared. It was found that in LB film form, the Q-band absorptions of these compounds were broadened and red-shifted slightly, comparing to in toluene solution. The NLO property of tetra-a-(2,4- di-tert-butylphenoxy) phthalocyanine vanadium and tetra-P- (potassium sulfonate ) phthalocyanine zinc was investigated in DMSO. Both of them showed obvious optical limiting effect. The former showed lower threshold while the later showed bigger transparent window in visible region.