The synthesis and photophysicochemical properties of low-symmetry zinc phthalocyanine analogues

The synthesis of a low-symmetry derivative, zinc mono-carboxy substituted phthalocyanine, ZnPc-COOH (4) has been reported. The photochemical and photophysical properties of ZnPc-COOH (4), ZnTMPyPc (5), ZnttbPc (6) and a previously synthesized low-symmetry derivative, ZnttbIPc (7), in various organic solvents are reported. The red-shifting of the spectra of 4 and 5 (relative to that of unsubstituted zinc phthalocyanine, ZnPc) is a function of the electron-donating sulfur-containing substituents attached to the periphery of the molecule. High triplet quantum yields (ФT) generally occur in response to substitution on the zinc phthalocyanine ring periphery. The highest ФT values and triplet lifetimes (τT) occur in DMSO for all derivatives as a result of the solventʹs high viscosity. The strongly electron-withdrawing imido fused ring of ZnttbIPc (7) stabilizes it against photo-oxidative degradation relative to the other derivatives.