Tandem mass spectrometry of π-expanded triphenylamine and N-heterotriangulene scaffolds

• Verfasst von: Kinzelmann, Marina [VerfasserIn]
• Verfasst von: Fröhlich, Nina [VerfasserIn]
• Verfasst von: Vogel, Alexander [VerfasserIn]
• Verfasst von: Kivala, Milan [VerfasserIn]
• Verfasst von: Drewello, Thomas [VerfasserIn]
• Titel: Tandem mass spectrometry of π-expanded triphenylamine and N-heterotriangulene scaffolds
• Titelzusatz: Radical cation versus silver(I) adduct
• Verf.angabe: Marina Kinzelmann, Nina Fröhlich, Alexander Vogel, Milan Kivala, Thomas Drewello
• E-Jahr: 2024
• Jahr: Sep 2024
• Umfang: 12 S.
• Illustrationen: Diagramme
• Fussnoten: Online veröffentlicht: 12. August 2024 ; Gesehen am 21.01.2025
• Titel Quelle: Enthalten in: Journal of mass spectrometry
• Ort Quelle: Bognor Regis [u.a.] : Wiley, 1995
• Jahr Quelle: 2024
• Band/Heft Quelle: 59(2024), 9 vom: Sept., Artikel-ID e5079, Seite 1-12
• ISSN Quelle: 1096-9888
• DOI: doi:10.1002/jms.5079
• Datenträger: Online-Ressource
• Sprache: eng
• Sach-SW: CH3Ag
• Sach-SW: energy-resolved collision-induced dissociation
• Sach-SW: radical cation
• Sach-SW: silver(I) adduct
• Sach-SW: π-extended triphenylamine and N-heterotriangulene
• K10plus-PPN: 1915213800

Abstract

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.