ABSTRACT
Asymmetrically substituted 5,10,15,20-tetraphenylporphyrin derivatives such as 5-(4-aminophenyl)10,15,20-triphenylporphine, 5-[4-(tyrosinylamino)phenyl]-10,15,20-triphenylporphine and 5-{4-[(N-tert-butoxycarbonyltyrosinyl)amino]phenyl}-10,15,20-triphenylporphine were synthesized. Their spectral and acid-base properties were studied. The acid-base interactions of the obtained compounds in the binary acetonitrile-perchloric acid and dimethyl sulfoxide-potassium cryptate (KOH[222]) systems were studied by spectrophotometry method. The effect of the nature of the solvent, concentration, pH value on the chemical activity of porphyrin was analyzed. Amino acid fragments affect the protolytic equilibrium of porphyrins in acidic and basic media.
ABSTRACT
Synthesis and identification of tetrakis-[5,6-bis(4-tert-butylphenyl)pyrazino] porphyrazine, tetra-(4-tert-butyl)phthalocyanine and octakis-(4-tert-butylphenyl)porphyrazine were carried out. Spectrophotometric method was used to study the spectral, acidic and fluorescence properties of the synthesized compounds. It was determined that the synthesized tert-butyl-substituted porphyrazines exhibit a high sensitivity of fluorescence to the molecule ionization. To understand the features of the spectral properties the geometry optimization and an analysis of energy levels and localization of highest occupied and lowest unoccupied molecular orbitals of the studied compounds were performed on the basis of density functional theory with the BP86 functional and the def2-TZVP basis set. The effect of substituents in molecular fragments of the macrocycle on the acidic and electro-optical properties of the studied compounds is revealed. Materials with pH-tunable fluorescence were designed.
