Synthesis, Characterization, And The Nature Of The Amino Metal Phthalocyanine And Its Derivatives

The particular physical and chemical properties of phthalocyanines (Pcs) have been paid close attention more and more in science field all over the word ever since 1907. As a kind of advanced functional materials in high-tech field, their applications are increasing steadily. PCS are widely applied in some sophisticated technique such as high-efficiency catalysis, biology simulation, super conducting materials, nonlinear optics, information storage, intellective recognition and so on. However, in certain extent their applications are limited due to the bad dissolution, difficulty in purification and hard synthesis of some PCS with special molecular configuration. In spite of these facts, We focus on our interst in the preparation of two classes of amino-phthalocyanines M( ) with excellent solubility, easy derivatization and high purity .Two kinds of pure teraamino-phthalocyanines M( ) have been synthesized, without using chromatographic purification, through two-step reaction from 4-nitro-o-phenyleneimine and 3-nitro-phthalic anhydride, respectively. In addition, their yield and purity are high. Both the PCS can dissolve easily in DMF or DMSO. The compounds synthesized were characterized by MS, 1HNMR, UV-vis and IR. The characterization results show that the dimmers can be formed easily in DMF. Amino-groups in the molecules present not only strong anti-oxidation stability, but also powerful electron-donating phenomenon towards phthalocyanine ring. Electron-donating phenomenon in the PCS synthesized from 3-nitro-phthalic anhydride was especially obviously. The amino-group in the PCS 'synthesized from 4-nitro-o-phenyleneimine displayed mainly thermodynamic spin stability, while the amino-group in the PCS synthesized from 3-nitro-phthalic anhydride showed mainly thermodynamic conjugation stability due to the existence of intramolecularhydrogen bonds in their molecules. The amino-group in the teraamino-phthalocyanine Cu(II), which synthesized from 3-nitro-phthalic anhydride, has the conversion trend from thermodynamic spin state to thermodynamic conjugation state. Teraphthalicimidino-phthalocyanine Cu(II) > Co (II) and teraphemethylimino-phthalocyanine Zn( II) have been prepared through acidylation and schiff reaction of some amino-phthalocyanines M(II), respectively. They are characterized using above methods. We analyzed qualitatively both the Q-band splitting in UV-vis spectra of Teraphthalicimidino-phthalocyanine Cu( II) , Co (II) and the UV-vis spectra of teraphemethylimino-phthalocyanine Zn (II), which is different in different solvent.To expect the future of amino-phthalocyanines M(II), it will be a kind of desired raw materials synthesizing the mercapto- containing PCS , which are a kind of desired self-assembling compounds. With the growth of mercapto-containing PCS fleetly in quantity and modification better in configuration, self-assembling technique will make a great progress to cause the further idealization of intellective devices.