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Synthesis of Octafluoroporphyrin
Angew. Chem., Int. Ed., 2016, 55, 5035-5039

DOI: 10.1002/anie.201511702
Chiranjeevulu Kashi, Chu-Chun Wu, Chi-Lun Mai, Chen-Yu Yeh,* Chi K. Chang*
Fluorinated porphyrinoids are interesting for many reasons. Apart from the fact that fluoroorganic molecules are of increasing importance as bioactives in life science, the electron-deficient nature of fluorinated porphyrinoids renders them ideal systems for modeling biomimetic mono-oxygenations, such as Fe/F20TPP and Mn/F20TPP for modeling cytochrome P450. With the current state of the art in porphyrin syntheses, most porphyrins, biological or otherwise, have either already been made or may be assembled without great difficulty. Yet, 2,3,7,8,12,13,17,18-octafluoroporphyrin (OFP) is one seemingly simple and fundamental compound that has eluded all synthetic attempts for over two decades. Fortunately, it is achieved in this study by condensation of two molecules of tetrafluoro-dipyrrylmethane-2-carboxaldehyde in the presence of magnesium(II) salts. The fluorinated dipyrrylmethane also gives 5,15-bis(pentafluorophenyl)-OFP (F18P) with a reasonable yield. Both Mg/OFP and Zn/F18P in the solid-state reveal an essentially flat structure. The fluoro groups impart as much as a 0.5 V anodic shift for porphyrin ring oxidation/reduction, as well as hypsochromic shifts in the UV-vis spectra.