SYNTHESIS AND PROPERTIES OF PERIPHERALLY AND NONPERIPHERALLY SUBSTITUTED ZINC AND MAGNESIUM PHTHALOCYANINES BASED ON 3/4-(4-BROMO-2-((4-METHOXYPHENYL)DIAZENYL)PHENOXY)PHTHALONITRILE

Abstract

The work describes the optimization of the procedure for the synthesis of 4-bromo-2-methoxyphenyldiazenylphenol, which is used as a nucleophile in the presence of 3- and 4-nitrophthalonitriles. The resulting 3-(4-bromo-2-((4-methoxyphenyl)diazenyl)phenoxy)- and 4-(4-bromo-2-((4-methoxyphenyl)diazenyl)phenoxy)phthalonitriles were used for template condensation with magnesium or zinc acetate. Methods for isolating and purifying the synthesized compounds are described. The structure and composition were confirmed using IR, 1H NMR and electron spectroscopy. Peripheral functionalization of macrocycle by a conjugate azochromophore fragment gives molecules phthalocyanine with special optical properties. This class of phthalocyanines containing an additional chromophore system in their composition is attractive for potential use not only as pigments and dyes traditional for phthalocyanine compounds, but also as chemical sensors, dye-sensitized solar cells and photosensitizers for PDT. The resulting nitriles and phthalocyanine complexes dissolve in chloroforms, toluene, THF, and DMF. The influence of the substituent location on the spectral properties of the obtained metal complexes (Zn, Mg) in organic solvents has been studied. For non-peripherally substituted metal phthalocyanines, acid-base properties are studied. To observe and study the acid-base effect, spectrophotometric titration of the trifluoroacetic acid complex in toluene is used. It is shown that the magnesium complex is more basic than the zinc complex. In this work, the luminescent properties are also studied and the quantum yields of singlet oxygen formation for synthesized complexes in THF are determined. The influence of the substituent location on the quantum yield of fluorescence, as well as on the generation of singlet oxygen, is noted in the work.