Electrospray Ionization (ESI) Tandem Mass Spectrometric Analysis of meso-Tetrakis(Heptafluoropropyl)Porphyrin

The results of an electrospray ionization (ESI(+) and ESI(−)) collision-induced fragmentation investigation of meso-tetrakis(heptafluoropropyl)porphyrin (TFHP) are reported. The fragmentation patterns of TFHP show, in both ionization modes, the formation of fragments with direct covalent meso-alkyl-to-β-linkages on elimination of HF. In addition, in the ESI(+) mode, the losses of perfluoroalkyl radicals are observed. A detailed analysis of the fragmentation patterns allows conclusions to be drawn on the identification of the fragment species. Comparable cyclized products were previously produced using radical-initiated solution-phase syntheses. The results presented will help to analyze meso-perfluoroalkyl-derivatized porphyrinic macrocycles that are becoming increasingly popular.