Perfluorinated porphyrazines. 3. Synthesis, spectral-luminescence and electrochemical properties of perfluorinated octaphenylporphyrazinatozinc(II)

[Display omitted] •Perfluorinated Zn(II) octaphenylporphyrazine was prepared.•Influence of perfluorination on electronic absorption and emission spectra was revealed.•Perfluorination strongly facilitates reduction of porphyrazine macrocycle and decreases its basic properties.•High efficiency of singlet oxygen generation was observed. Octakis(pentafluorophenyl)porphyrazinatozinc(II), [ZnPAF40], has been prepared by template cyclotetramerization of perfluorinated α,β-dicyanostylbene in the presence of ZnCl2 in a melt. Influence of perfluorination of phenyl rings on spectral, electrochemical and acid-base properties of porphyrazine macrocycle is revealed by comparison with octaphenylporphyrazinatozinc(II), [ZnPA], which was prepared similarly from trans-α,β-dicyanostylbene. B3LYP DFT calculations show that perfluorination of phenyl rings stabilizes the frontier molecular orbitals of the porphyrazine macrocycle and slightly increases the HOMO-LUMO gap. As a result the reduction of the macrocycle is strongly facilitated and observed for [ZnPAF40] at 0.26 V vs Ag/AgCl, by 0.56 V in the less negative region as compared to [ZnPA]. Perfluorination leads to hypsochromic shift of the Q-band (lowest ππ* transition) in the electronic absorption spectra from 633 nm for [ZnPA] to 623 nm for [ZnPAF40] and increases the fluorescence quantum yield ФF from 0.12 to 0.19, respectively (values in THF). [ZnPAF40] has higher efficiency in generation of singlet oxygen (ФΔ = 0.60) than [ZnPA] (ФΔ = 0.37) (in THF). Introduction of 40 fluorine atoms decreases the basicity of the porphyrazine macrocycle almost by 3 orders of magnitude according to spectrophotometric titration study in CH2Cl2-CF3COOH medium.