SPECTROPHOTOMETRIC STUDY OF ACID-BASE PROPERTIES OF SPATIAL-DISTORTED DERIVATIVES OF PORPHYRINS IN ACETONITRILE

Spectrophotometric titration method was used to study the acidic properties of: 5,10,15,20-tetrakis(thienyl-2-yl)-2,3,7,8,12,13,17,18-octaethylporphyrin (I), 5,10,15,20-tetrakis(4’-t-butylphenyl)-2,3,7,8,12,13,17,18-octaethylporphyrin (II), 5,10,15,20-tetrakis(3,5-di-t-butylphe-nyl)-2,3,7,8,12,13,17,18-octaethylporphyrin (III), 5,10,15,20-tetraphenyl-2,3,7,8,12,13,17,18-octaethylporphyrin (IV), 5,15-bis(4’-methoxyphenyl)-10,20-bis(4-nitro-phenyl)-2,8,12,18-tetrame-thyl-3,7,13,17-tetraarylporphyrin (V), 5,15-bis(4’-methoxyphenyl)-10,20-diphenyl-2,3,7,8,12,13, 17,18-octaethylporphyrin (VI), 5,15-bis(4’-methoxyphenyl)-2,8,12,18-tetramethyl-3,7,10,13,17,20-hexaethylporphin (VII), 5,10,15,20-tetrakis(4’-methoxyphenyl)-2,3,7,8,12,13,17,18-octaethylpor-phyrin (VIII) in the presence of a deprotonated agent, 1,8-diazabicyclo[5.4.0] undec-7-ene, in acetonitrile. Under deprotona-tion two families of spectral curves in the absorption spectra, having its own system of isobes-tic points, are formed. Electron absorption spectrum of molecular form transforms gradually into the spectrum of the final form of dianion with titrant concentration increase. Determina-tion of the coordinates of the inflection (and the corresponding concentration of DBU) on the titration curve allowed us to distinguish two areas in the electron absorption spectra of the reaction system, which are likely belong to the first and second steps of deprotonation, name-ly, to the formation of mono- and dianionic forms (HP– and P2–) of the compound. Spectral characteristics of the ionized forms and combined ionization constant for the first and second steps (lgКа1 and lgКа2) were revealed. At the first step in the order of decreasing acidic prop-erties of the ligands the compounds form a series of: III< V< VIII< VI < VII< II< IV < I; at the second step in decreasing order of the acidic properties of the ligands the compounds form a series of:.III < V < VI < II

Key words: porphyrins, acid-base properties 1,8- diazabicyclo[5.4.0] undec-7- ene, acetonitrile

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