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Journal Article

Photooxygenation and gas-phase reactivity of multiply threaded pseudorotaxanes

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Warnke,  Stephan
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Pagel,  Kevin
Institut für Chemie und Biochemie, Freie Universität Berlin;
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Citation

Nowosinski, K., Warnke, S., Pagel, K., Komáromy, D., Jiang, W., & Schalley, C. A. (2016). Photooxygenation and gas-phase reactivity of multiply threaded pseudorotaxanes. Journal of Mass Spectrometry, 51(4), 269-281. doi:10.1002/jms.3746.


Cite as: https://hdl.handle.net/11858/00-001M-0000-002A-50B5-D
Abstract
The solution-phase photooxygenation of multiply threaded crown/ammonium pseudorotaxanes containing anthracene spacers is monitored by electrospray ionization Fourier-transform ion-cyclotron-resonance (ESI-FTICR) mass spectrometry. The oxygenated pseudorotaxanes are mass-selected and fragmented by infrared multiphoton dissociation (IRMPD) and/or collision-induced dissociation (CID) experiments and and their behavior compared to that of the non-oxygenated precursors. [4+2]Cycloreversion reactions lead to the loss of O, when no other reaction channel with competitive energy demand is available. Thus, the release of molecular oxygen can serve as a reference reaction for the energy demand of other fragmentation reactions such as the dissociation of the crown/ammonium binding motifs. The photooxygenation induces curvature into the initially planar anthracene and thus significantly changes the geometry of the divalent, anthracene-spacered wheel. This is reflected in ion-mobility data. Coulomb repulsion in multiply charged pseudorotaxanes assists the oxygen loss as the re-planarization of the anthracene increases the distance between the two charges.