[2.2]Paracyclophane bis(pyridine)-based metallosupramolecular rhombs in the gas phase: Competitive cleavage of non-covalent and weak covalent bonds

  • Yvonne Lorenz
  • Jana Anhäuser
  • Arne Lützen
  • Marianne EngeserEmail author
Focus: Honoring Helmut Schwarz's Election to the National Academy of Sciences: Research Article


The gas-phase fragmentation behavior of self-assembled metallo-supramolecular rhombs based on an unusual chiral [2.2]paracyclophane bis(pyridine) ligand is studied by collision-induced dissociation mass spectrometry. The fragmentation patterns strongly depend on the charge state of the respective mass-selected aggregate. For the doubly charged ions, simple symmetric fragmentation is observed in full accordance with previous results reported for related metallo-supramolecular species. The triply charged species cleaves unsymmetrically which can be rationalized by a preferred formation of ions with low charge density. CID of the quadruply charged rhomb reveals a complex fragmentation. Besides ligand oxidation to the radical cation, facile cleavage of the central covalently bound part of the [2.2]paracyclophane ligand takes place which is even preferred over rupture of the weak dative pyridine-Pd bond.


Metallo-supramolecular chemistry Weak covalent bonds Chiral Collision-induced dissociation Self-assembly Rhombs 



We thank the Studienstiftung des deutschen Volkes for a doctoral scholarship and the Bonn International Graduate School of Chemistry for an international research scholarship (J.A.), and the Deutsche Forschungsgemeinschaft (SFB 813) for financial support.


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© American Society for Mass Spectrometry 2019

Authors and Affiliations

  1. 1.Kekulé-Institute of Organic Chemistry and BiochemistryUniversity of BonnBonnGermany

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