title: ESI-MS/MS of expanded porphyrins: a look into their structure and aromaticity.
abstract: Electrospray mass spectrometry/mass spectrometry was used to investigate the gas-phase properties of protonated expanded porphyrins, in order to correlate those with their structure and conformation. We have selected five expanded meso-pentafluorophenyl porphyrins, respectively, a pair of oxidized/reduced fused pentaphyrins (22 and 24 π electrons), a pair of oxidized/reduced regular hexaphyrins (26 and 28 π electrons) and a regular doubly N-fused hexaphyrin (28 π electrons). The gas-phase behavior of the protonated species of oxidized and reduced expanded porphyrins is different. The oxidized species (aromatic Hückel systems) fragment more extensively, mainly by the loss of two HF molecules. The reduced species (Möbius aromatic or Möbius-like aromatic systems) fragment less than their oxidized counterparts because of their increased flexibility. The protonated regular doubly fused hexaphyrin (non-aromatic Hückel system) shows the least fragmentation even at higher collision energies. In general, cyclization through losses of HF molecules decreases from the aromatic Hückel systems to Möbius aromatic or Möbius-like aromatic systems to non-aromatic Hückel systems and is related to an increase in conformational distortion. Copyright © 2016 John Wiley & Sons, Ltd.
authors.affiliation: QOPNA-Mass Spectrometry Laboratory, Department of Chemistry, University of Aveiro, Campus de Santiago, 3810-193, Aveiro, Portugal.
authors.forename: Catarina Iv
authors.initials: CI
authors.lastname: Ramos
authors.affiliation: QOPNA-Organic Chemistry Laboratory, Department of Chemistry, University of Aveiro, Campus de Santiago, 3810-193, Aveiro, Portugal.
authors.forename: Flávio
authors.initials: F
authors.lastname: Figueira
authors.affiliation: Centro de Biotecnologia, Universidade Federal do Rio Grande do Sul, Av. Bento Gonçalves 9500, CP 15005, Porto Alegre, 91500-970, RS, Brazil.
authors.forename: Marcelo D
authors.initials: MD
authors.lastname: Polêto
authors.affiliation: QOPNA-Mass Spectrometry Laboratory, Department of Chemistry, University of Aveiro, Campus de Santiago, 3810-193, Aveiro, Portugal.
authors.forename: Francisco Ml
authors.initials: FM
authors.lastname: Amado
authors.affiliation: Centro de Biotecnologia, Universidade Federal do Rio Grande do Sul, Av. Bento Gonçalves 9500, CP 15005, Porto Alegre, 91500-970, RS, Brazil.
authors.forename: Hugo
authors.initials: H
authors.lastname: Verli
authors.affiliation: QOPNA-Organic Chemistry Laboratory, Department of Chemistry, University of Aveiro, Campus de Santiago, 3810-193, Aveiro, Portugal.|Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001, Lisboa, Portugal.
authors.forename: João Pc
authors.initials: JP
authors.lastname: Tomé
authors.affiliation: QOPNA-Organic Chemistry Laboratory, Department of Chemistry, University of Aveiro, Campus de Santiago, 3810-193, Aveiro, Portugal.
authors.forename: M Graça Pms
authors.initials: MG
authors.lastname: Neves
mesh_terms: D054879:Halogenation; D006841:Hydrocarbons, Aromatic / Q000737:chemistry; D010084:Oxidation-Reduction; D010946:Plants, Medicinal / Q000737:chemistry*; D011166:Porphyrins / Q000737:chemistry*; D011522:Protons; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D053719:Tandem Mass Spectrometry / Q000379:methods
chemical_list: D006841:Hydrocarbons, Aromatic; D011166:Porphyrins; D011522:Protons
keywords: Hückel systems; Möbius systems; electrospray mass spectrometry; gas-phase; protonated expanded porphyrins; structure/aromaticity