Coordination and acid-base properties of meso-nitro derivatives of β-octaethylporphyrin

Spectrophotometric method is used to study the acid-base and coordination properties of a series of porphyrins with a continuously increasing degree of macrocycle deformation resulting from the introduction of strong electron - withdrawing substituents: 2,3,7,8,12,13,17,18-octaethylporphyrin (1), 5-nitro-2,3,7,8,12,13,17,18-octaethylporphyrin (2), 5,15-dinitro-2,3,7,8,12,13,17,18-octaethylporphyrin (3), 5,10,15-trinitro-2,3,7,8,12,13,17,18-octaethylporphyrin (4), and 5,10,15,20-tetranitro-2,3,7,8,12,13,17,18-octaethylporphyrin (5). It is found that the values of total basicity constants obtained for the investigated compounds consistently diminish with an increase in the number of meso-substituents: 11.85 (1) > 10.45 (2) > 10.31 (3) > 10.23 (4) > 9.56 (5). The values of the combined acidity constants of porphyrins (4-5) obtained in acetonitrile-DBU system at 298 K are pK(a) = 10.90 and 10.40 respectively. The reaction of complex formation between the porphyrins and their dianionic forms with zinc acetate was studied. It is shown that two opposing factors, the steric and electronic effects of the substituents, change the acid-base and coordination properties of the above series of compounds.