Electrochemical and Spectroscopic Characterization of Manganese(III) Dodecaphenylporphyrin Derivatives and X-ray Structural Determination of Chloro(5,10,15,20-tetrakis(pentafluorophenyl)-2,3,7,8,12,13,17,18- octaphenylporphyrinato)-manganese(III). Formation of a Manganese(IV) Species by Ozone and Electrochemical Oxidation

The electrochemistry of nine different manganese(III) dodecaphenylporphyrins containing halogen or CF3 groups on the phenyl rings of the porphyrin macrocycle is reported. Six of the compounds were previously synthesized while three of the derivatives, (DPPF8 )MnCl, (DPPCl12 )MnCl and (DPPF28 )MnCl, are reported for the first time in this study. Each of the nine compounds was characterized in its neutral form by UV-visible and 1H and 19F NMR spectroscopy and in its singly oxidized form by UV-visible and ESR spectroscopy after reaction with ozone. An X-ray crystal structure of (DPPF20 )MnCl (C92H40N4F20 MnCl·2CHCl3 ·0.25H2O) was also obtained. The compound crystallized in the monoclinic space group P21/c with cell dimensions a -17.258(3) Å, b = 28.593(6) Å, c = 17.476(4) Å, β= 107.16(2)°, and Z = 4. It is nonplanar and adopts a saddle/ruffle hybridized macrocycle conformation