Investigation of the demetallation of 10-aryl substituted synthetic chlorins under acidic conditions

Abstract

The acidic demetallation of a series of sparsely substituted Zn(II) chlorins is reported. The chlorins were functionalized in the 10-position with substituents ranging from strongly electron donating mesityl and p-methoxyphenyl to electron-withdrawing p-nitrophenyl and pentafluorophenyl groups. The demetallation kinetics were investigated using UV-Visible absorption spectroscopy. Demetallation was carried out by exposing the metallochlorins dissolved in CH₂Cl₂ to an excess of trifluoroacetic acid. Reasonable correlation was found between the Hammett constant of the 10-substituent and the rate constant of the loss of the metal ion. The largest differences were observed between the p-methoxyphenyl and p-nitrophenyl-substituted Zn(II) chlorins, undergoing loss of Zn(II) with pseudo first order rate constants of 0.0789 × 10^-3 and 3.70 × 10^-3 min^-1, respectively. Taken together, these data establish the dramatic influence even subtle changes can have in altering the electronic properties of chlorins, which in turn impacts metallochlorin function.