Design, synthesis, and properties of azaporphyrin phosphorus complexes

Azaporphyrinoids, such as phthalocyanines (Pcs), tetraazaporphyrins (TAPs), and tetrabenzotriazacorroles (TBCs) are some of the most well-known and successful artificial dyes and pigments in modern material chemistry. In this article, on modifying optical properties of azaporphyrins, we have proposed a novel "π electron-unmodified" approach by utilizing the unique properties of the phosphorus (V) ion with simple macrocyclic ligands. Although the azaporphyrin phosphorus(V) complexes could be synthesized via simple synthetic procedures, they revealed unique optical properties not seen in other metalloazaporphyrinoids reported to date, such as intense absorption and fluorescence bands beyond 1,000 nm, broad absorption bands across the entire UV-vis region, and high singlet oxygen quantum yields. The combination of peripheral substituents and theoretical calculations was effective for the rational design of optical properties in the UV-vis-near-IR region, which is also demonstrated. The practical synthesis, purification, and characterization of azaporphyrins have also been described for general organic synthetic chemists. calculation.