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

Kinzelmann M, Fröhlich N, Vogel A, Kivala M, Drewello T (2024)

Publication Type: Journal article

Publication year: 2024

Journal

Book Volume: 59

Article Number: e5079

Journal Issue: 9

DOI: 10.1002/jms.5079

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.

Authors with CRIS profile

Involved external institutions

Ruprecht-Karls-Universität Heidelberg Germany (DE)

How to cite

APA:

Kinzelmann, M., Fröhlich, N., Vogel, A., Kivala, M., & Drewello, T. (2024). Tandem mass spectrometry of π-expanded triphenylamine and N-heterotriangulene scaffolds: Radical cation versus silver(I) adduct. Journal of Mass Spectrometry, 59(9). https://doi.org/10.1002/jms.5079

MLA:

Kinzelmann, Marina, et al. "Tandem mass spectrometry of π-expanded triphenylamine and N-heterotriangulene scaffolds: Radical cation versus silver(I) adduct." Journal of Mass Spectrometry 59.9 (2024).

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