Imidazole and imidazolium porphyrins: Gas-phase chemistry of multicharged ions

Catarina I.V. Ramos, Patrícia M.R. Pereira, M. Graça Santana-Marques, Rodrigo De Paula, Mário M.Q. Simões, M. Graça P.M.S. Neves, José A.S. Cavaleiro

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Electrospray ionization mass spectrometry/mass spectrometry in the positive ion mode was used to investigate the gas-phase chemistry of multicharged ions from solutions of porphyrins with 1,3-dimethylimidazolium-2-yl (DMIM) and 1-methylimidazol-2-yl (MIm) meso-substituents. The studied compounds include two free bases and 12 complexes with transition metals (Cu(II), Zn(II), Mn(III), and Fe(III)). The observed multicharged ions are either preformed or formed during the electrospraying process by reduction or protonation and comprise closed-shell and hypervalent mono-radical and bi-radical ions. The observed extensive and abundant fragmentation of the DMIM and MIm meso-substituents is a characteristic feature of these porphyrins. Fragments with the same mass values can be lost from the meso-substituents either as charged or neutral species and from closed-shell and hypervalent radical ions. Reduction processes are observed for both the free bases and the metallated DMIM porphyrins and occur predominantly by formation of hypervalent radicals that fragment, at low energy collisions, by loss of methyl radicals with formation of the corresponding MIm functionalities. These findings confirm that, when using electrospray ionization, reduction is an important characteristic of cationic meso-substituted tetrapyrrolic macrocycles, always occurring when delocalization of the formed hypervalent radicals is possible. For the Fe(III) and Mn(III) complexes, reduction of the metal centers is also observed as the predominant fragmentation of the corresponding reduced ions through losses of charged fragments testifies. The fragmentation of the closed-shell ions formed by protonation of the MIm porphyrins mirrors the fragmentation of the closed-shell ions of their DMIM counterparts.

Original languageEnglish
Pages (from-to)371-379
Number of pages9
JournalJournal of Mass Spectrometry
Issue number5
StatePublished - May 2014


  • electrospray mass spectrometry
  • gas-phase chemistry
  • imidazole porphyrins
  • imidazolium porphyrins
  • multicharged ions


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