Tetrapyrazinoporphyrazines with different number of peripheral pyridyl rings: Synthesis, photophysical and photochemical properties

Zinc tetrapyrazinoporphyrazines comprising different numbers of pyridin-2-yl and tert-butylsulfanyl substituents were prepared by the statistical condensation of two precursors – 5,6-bis(tert-butylsulfanyl)pyrazine-2,3-dicarbonitrile (A) and 5,6-dipyridin-2-yl-pyrazine-2,3-dicarbonitrile (B). The ensuing zinc tetrapyrazinoporphyrazines were chromatographically separated on silica column and characterized. Adjacent (AABB) and opposite (ABAB) isomers were not separated. The prepared zinc tetrapyrazinoporphyrazines did not differ in their Q-band position but the B-band position was shifted hypsochromically for compounds bearing more pyridyl units; in addition, a weak band at 450–520 nm decreased with increasing number of pyridyl substituents. Singlet oxygen quantum yields (ΦΔ in the range 0.69–0.53) decreased with increasing number of pyridyl units on the macrocyclic core, while fluorescence quantum yields showed the reverse tendency (ΦF in the range 0.22–0.26).