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Perfluorinated porphyrazines. 3. Synthesis, spectral-luminescence and electrochemical properties of perfluorinated octaphenylporphyrazinatozinc(II)
Journal of Fluorine Chemistry ( IF 1.9 ) Pub Date : 2018-08-16 , DOI: 10.1016/j.jfluchem.2018.08.006
Irina A. Lebedeva (Yablokova) , Svetlana S. Ivanova , Veronika Novakova , Yuriy A. Zhabanov , Pavel A. Stuzhin

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.



中文翻译:

全氟卟啉。3.全氟八苯基卟啉叠氮锌(II)的合成,光谱发光和电化学性质

通过在熔体中存在ZnCl 2的情况下,对全氟化α,β-二氰基苯乙烯基苯进行模板环四聚,可以制备八(五氟苯基)卟啉锌锌(II),[ZnPAF 40 ] 。通过与类似的由反式α,β-二氰基丁二烯制得的八苯基卟啉叠氮锌(II)[ZnPA]的比较,揭示了苯环的全氟化对卟啉大环化合物的光谱,电化学和酸碱性质的影响。B3LYP DFT计算表明,苯环的全氟化作用可稳定卟啉大环分子的前沿分子轨道,并略微增加HOMO-LUMO间隙。结果,[ZnPAF 40与[ZnPA]相比,在负值较小的区域中,相对于Ag / AgCl在0.26 V下的电压降低了0.56V。全氟化导致从633纳米为[ZnPA]的Q带的蓝移(最低ππ*跃迁)在电子吸收光谱为[ZnPAF 623纳米40 ],并增加荧光量子产率Ф ˚F分别为0.12〜0.19, (以THF为单位的值)。[ZnPAF 40 ]具有产生单线态氧的(Ф更高效率Δ  = 0.60)比[ZnPA](Ф Δ  = 0.37)(在THF中)。根据CH 2 Cl 2 -CF 3中的分光光度滴定研究,引入40个氟原子会使卟啉大环的碱性降低了近三个数量级。COOH介质。

更新日期:2018-08-16
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