Photooxygenation and gas-phase reactivity of multiply threaded pseudorotaxanes

K. Nowosinski, S. Warnke, K. Pagel, D. Komáromy, W. Jiang, C.A. Schalley – 2016

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 compared to the non-oxygenated precursors. [4+2]Cycloreversion reactions lead to the loss of O2, when no other reaction channel with competitive energy-demand is available. Thus, the oxygen molecule 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.

Titel
Photooxygenation and gas-phase reactivity of multiply threaded pseudorotaxanes
Verfasser
K. Nowosinski, S. Warnke, K. Pagel, D. Komáromy, W. Jiang, C.A. Schalley
Datum
2016
Kennung
10.1002/jms.3746
Zitierweise
J. Mass Spectrom. 2016, 51, 269-281
Art
Text
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