The Diradical-Dication Strategy for BODIPY- and Porphyrin-Based Dyes with Near-Infrared Absorption Maxima from 1070 to 2040 nm.

Four stable boron dipyrromethene (BODIPY)- and porphyrin-based bis-arylamine diradical dications were synthesized by two-electron oxidation of their neutral molecules. The two BODIPY-based dications have open-shell singlet ground states. UV/Vis absorption spectra of all four dications showed large redshifts in the NIR region compared to their neutral precursors with absorption maxima at 1274 and 1068 nm for the two BODIPY-based dications and 1746 and 2037 nm for the two porphyrin-based dications. Thus, two new types of NIR dyes with longer wavelengths are provided by the diradical-dication strategy, which can be applied for the generation of other NIR dyes with a range of different chromophores and auxochromes.