Syntheses And Properties Of Several Novel Tetra-substituted Metal Phthalocyanines

As a kind of important functional materials, phthalocyanines have been widely used in many high-tech fields, such as solar energy cells, chemistry sensors, electrochromic substances, laser recorder materials, nonlinear optics and so on. In different application fields, the structure of phthalocyanine molecule needs to be modified to obtain the required physical and chemical properties, for example, different substituent groups and center metal was induced into the phthalocyanine ring.The main works and results of this paper are summarized as follows:1.Phthalocyaninezinc substituted with schiff basic was synthesized by liquid phase method. First, the precursor of metallophthalocyanines was synthesized by nucleophilic reaction, the precursor is 4-(4-Phenyliminomethyl-phenoxy)-phthalonitrile, which is characterized by Elemental Analysis, IR, 1H NMR. Then the substituted phthalocyaninezinc was synthesized through"DBU method", which is characterized by mass spectrum. It was found that the products were the mixture containing five kinds of phthalocyaninezinc, they are three kinds of unsymmetrical substituted phthalocyaninezinc and two kinds of symmetrical substituted phthalocyaninezinc. So it is concluded that phthalocyaninezinc substituted with schiff base is unstable under the reaction temperature.2. Metalphthalocyanine substituted with schiff basic reduced were prepared by liquid phase method. First, after two schiff bases were reduced, three precursor of metallophthalocyanines were synthesized by nucleophilic reaction, which are 4-(4-Phenylaminomethyl-phenoxy)-phthalonitrile, 3-(4-Phenylaminomethyl-phenoxy)phthal- onitrile and 4-[4-(Thiazol-2-ylaminomethyl)-phenoxy]-phthalonitrile. They were characterized by Elemental Analysis, IR and 1H NMR. Then nine kinds of substituted metallophthalocyanines were synthesized through"DBU method": tetra-β-(4-Phenylaminomethyl-phenoxy)metallophthalocyanines, tetra-α-(4-Phenylaminomet- hyl-phenoxy)metallophthalocyanines, tetra-β-(4-(Thiazol-2- ylaminomethyl)- phenoxy) metallophthalocyanines. They were characterized by Elemental Analysis, IR,1H NMR, UV-Vis spectra and mass spectrum.3. This paper studies the UV-Vis spectra and fluorescence spectrum of the synthesized metallophthalocyanines. The effects of the positions of substituted group, center metal and the solution onλmax in Q-band were discussed. The results indicate that theλmax in Q-band of the synthesized metallophthalocyanines shift to red region in contrast to the correspond non-substituted metallophthalocyanines. The different center metal have some effects on theλmax of Q-band of the metallophthal ocyanines; the kinds of solution has a few effects on the λmax of Q-band; The effects of the positions of substituted group onλmax in Q-band were much more distinct, Theλmax in Q-band ofαsubstituted metallophthalocyanines red-shift extent was much more great than theβsubstituted metallophthalocyanines. Furthermore, The effects of the center metals onλemmax and intensity of fluorescence were discussed. The results show that the order of theλemmax is Zn(II) >Ni(II) >Cu(II) > Co(II); When the center metal is Zn(II) and Ni(II), phthalocyanines have strong fluorescence intensity; When the center metal is Cu(II) and Co(II), phthalocyanines have weak fluorescence intensity.