Stability of Odd- Versus Even-Electron Gas-Phase (Quasi)Molecular Ions Derived from Pyridine-Substituted N-Heterotriangulenes

Beitrag in einer Fachzeitschrift


Details zur Publikation

Autor(en): Hitzenberger J, Dral PO, Meinhardt U, Clark T, Thiel W, Kivala M, Drewello T
Zeitschrift: ChemPlusChem
Verlag: WILEY-V C H VERLAG GMBH
Jahr der Veröffentlichung: 2017
Band: 82
Heftnummer: 2
Seitenbereich: 204-211
ISSN: 2192-6506


Abstract

Electrospray ionisation of N-heterotriangulenes (i.e., dimethyl-methylene-bridged triphenylamines) with up to three pyridyl groups at their periphery, produces the true radical cation ([M](+center dot)) and the protonated molecule ([M+H](+)) simultaneously. These ions are studied as model systems to illustrate the stability alternation of odd-versus even-electron ions in energy-dependent collision-induced dissociation (CID) experiments. All ions show the same fragmentation pattern, the consecutive loss of three methyl radicals ((CH3)-C-center dot) from the dimethylmethylene bridges of the central triangulene core. [M](+center dot) ions dissociate at much lower collision energies than their [M+H](+) counterparts. The radical cation forms a singlet fragment with an extended aromatic system that is energetically favoured. Ab initio and density functional theory calculations support this interpretation and allow the assignment of the electronic structure of the fragment ions. Consecutive collision-induced dissociations provide a better match with theory when studied with an ion trap, rather than a linear quadrupole. This is attributed to the resonant nature of the excitation of intermediate ions.


FAU-Autoren / FAU-Herausgeber

Clark, Timothy apl. Prof. Dr.
Computer-Chemie-Centrum
Drewello, Thomas Prof. Dr.
Professur für Physikalische Chemie
Hitzenberger, Jakob
Professur für Physikalische Chemie
Kivala, Milan Prof. Dr.
Lehrstuhl für Organische Chemie I
Meinhardt, Ute
Lehrstuhl für Organische Chemie I


Autor(en) der externen Einrichtung(en)
Max-Planck-Institut für Kohlenforschung (MPI KoFo) / Max Planck Institute for Coal Research


Zitierweisen

APA:
Hitzenberger, J., Dral, P.O., Meinhardt, U., Clark, T., Thiel, W., Kivala, M., & Drewello, T. (2017). Stability of Odd- Versus Even-Electron Gas-Phase (Quasi)Molecular Ions Derived from Pyridine-Substituted N-Heterotriangulenes. ChemPlusChem, 82(2), 204-211. https://dx.doi.org/10.1002/cplu.201600416

MLA:
Hitzenberger, Jakob, et al. "Stability of Odd- Versus Even-Electron Gas-Phase (Quasi)Molecular Ions Derived from Pyridine-Substituted N-Heterotriangulenes." ChemPlusChem 82.2 (2017): 204-211.

BibTeX: 

Zuletzt aktualisiert 2019-03-06 um 11:05