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Tandem mass spectrometry of π-expanded triphenylamine and N-heterotriangulene scaffolds: Radical cation versus silver(I) adduct

Triphenylamine (TPA) and N-heterotriangulene (N-HTA) scaffolds with up to three oligophenyl extensions are investigated by electrospray ionization (tandem) mass spectrometry (ESI-[MS/]MS). Due to their low oxidation potentials, all molecules readily form radical cations in the electrospray process....

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Bibliographic Details
Main Authors: Kinzelmann, Marina (Author) , Fröhlich, Nina (Author) , Vogel, Alexander (Author) , Kivala, Milan (Author) , Drewello, Thomas (Author)
Format: Article (Journal)
Language:English
Published: Sep 2024
In: Journal of mass spectrometry
Year: 2024, Volume: 59, Issue: 9, Pages: 1-12
ISSN:1096-9888
DOI:10.1002/jms.5079
Online Access:Verlag, kostenfrei, Volltext: https://doi.org/10.1002/jms.5079
Verlag, kostenfrei, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/jms.5079
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Author Notes:Marina Kinzelmann, Nina Fröhlich, Alexander Vogel, Milan Kivala, Thomas Drewello
Description
Summary:Triphenylamine (TPA) and N-heterotriangulene (N-HTA) scaffolds with up to three oligophenyl extensions are investigated by electrospray ionization (tandem) mass spectrometry (ESI-[MS/]MS). Due to their low oxidation potentials, all molecules readily form radical cations in the electrospray process. The energy-resolved collision-induced dissociation behaviour of the molecular ions is contrasted to that of the silver(I) adducts. Complexation with Ag(I) leads to the expected [1:1] and [2:1] complexes (MAg+ and M2Ag+); however, even [1:2] complexes (MAg22+) can be detected for molecules with two and three large π-expansions to allow stabilization of two charges. The TPA scaffolds decompose only at high collision energies through the loss of peripheral tert-butyl groups. A general mechanism for this is proposed commencing with a methyl loss and followed by the release of isobutene and butyl radical moieties. The N-HTA-based scaffolds are considerably less stable and molecular ions fragment at low collision energies. This is caused by the facile loss of methyl radicals from the dimethylmethylene-bridged triangulene core. In contrast, complexation with Ag+ leads to a dramatic stabilization. Most interestingly, dissociation eventually proceeds via the loss of neutral AgCH3, which is indicative of strong bidentate, tweezer-like bonding of Ag+ to the molecules.
Item Description:Online veröffentlicht: 12. August 2024
Gesehen am 21.01.2025
Physical Description:Online Resource
ISSN:1096-9888
DOI:10.1002/jms.5079

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