Charge‐State‐Dependent Fragmentation of [2.2]Based Metallosupramolecular Cyclic Helicates in the Gas Phase. Issue 11 (25th November 2020)

• Record Type: Journal Article
• Authors: Anhäuser, Jana; Lützen, Arne; Engeser, Marianne
• Is Part Of: ChemPlusChem. Volume 85:Issue 11(2020)
• Page Start: 2528
• Page End: 2533
• Publication Date: 2020-11-25
• Subjects: collision-induced dissociation -- cyclic helicates -- gas-phase fragmentation -- self-assembly -- supramolecular chemistry; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/cplu.202000697
• Languages: English
• ISSNs: 2192-6506

Abstract

Abstract: A detailed mass‐spectrometric study provides insight into the gas‐phase fragmentation pathways of a cyclic helicate selectively built from four iron(II) centers and six [2.2]cyclophane‐based ligands through the subcomponent self‐assembly approach. The charge state of the precursor ion, i. e., the number of triflate anions accompanying the metallo‐supramolecular core, has a strong influence on the observed fragmentations. The triply charged ion shows loss of a neutral ligand whereas ions of higher charge fragment by up to three different charge‐separating pathways to minimize the charge density of the ions. Additional subsequent fragmentations of highly charged fragment ions include redox processes as well as splitting of the unusual paracyclophane backbone. Abstract : Charge matters ! The peculiar structure of a metallo‐supramolecular cyclic helicate leaves unique traces in its gas‐phase fragmentation pattern, yet the charge state of the selected precursor ion should not be disregarded. It is by far the dominating factor. Triply charged ions prefer simple ligand expulsion, while charge‐separating cleavage of the aggregates prevails for higher charge states in addition to redox processes and ligand splitting.