Stability of Odd- Versus Even-Electron Gas-Phase (Quasi)Molecular Ions Derived from Pyridine-Substituted N-Heterotriangulenes
Hitzenberger J, Dral PO, Meinhardt U, Clark T, Thiel W, Kivala M, Drewello T (2017)
Publication Status: Published
Publication Type: Journal article
Publication year: 2017
Journal
Publisher: WILEY-V C H VERLAG GMBH
Book Volume: 82
Pages Range: 204-211
Journal Issue: 2
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.
Authors with CRIS profile
Jakob Hitzenberger
Professur für Physikalische Chemie
Ute Meinhardt
Lehrstuhl für Organische Chemie I
Timothy Clark
Computer-Chemie-Centrum (CCC)
Milan Kivala
Lehrstuhl für Organische Chemie I
Thomas Drewello
Professur für Physikalische Chemie
Involved external institutions
Germany (DE)How to cite
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://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.
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