Narrow Results

The main synthetic approaches for the preparation of porphyrazines are outlined. In addition, some structural and spectroscopic properties, especially the UV-vis absorption profiles emanating from their peripheral functionalization, the modification of the tetraazaporphyrin skeleton or the arrangement of macrocycles in a supramolecular manner, are discussed. Cyclotetramerization of appropriate dinitrile derivatives or modification of peripheral substituents on porphyrazines constitute the main synthetic routes. Moreover, the use of special templates, as well as different intermediates or nonpyrrolic precursors, are tools for the attainment of azaporphyrin analogues of distinct nature and unusual characteristics.

Unprecedentedly large subporphyrazines (SubPz) with dibenzoquinoxalino-fusion and peripheral phenyl substitution were prepared by the cyclization of perfluorated or non-fluorous polyphenyl-substituted quinoxaline dinitriles and characterized by spectroscopic techniques. The compounds suitability to act as photosensitizers was explored by wavelength-specific induction of singlet oxygen luminescence and was shown to be excellent. Determination of ¹O₂-quantum yields suggests that fluorine substitution enhances the photosensitization efficiencies of the SubPz. On the other hand, cyclic voltammetry reveals an increase of irreversible reductive processes in case of the fluorinated SubPz.