Abstract
We have established a convenient method for the base-promoted direct
amination of β-unsubstituted 5,15-diazaporphyrins (DAPs) with
secondary and primary amines to produce 3,7,13,17-tetraamino- and
3-amino-DAPs, respectively, regioselectively. The amino groups
attached at the periphery cause significant red shifts of the
absorption bands as a result of their perturbation of the HOMO and/or
LUMO in the DAP π-system. The palladium complex of a
3,7,13,17-tetrakis(diphenylamino)-DAP generated singlet oxygen in high
yield under irradiation with near-infrared light.