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Gas-phase fragmentation of 1-adamantylbisimidazolium salts and their complexes with cucurbit[7]uril studied using selectively 2H-labeled guest molecules

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dc.title Gas-phase fragmentation of 1-adamantylbisimidazolium salts and their complexes with cucurbit[7]uril studied using selectively 2H-labeled guest molecules en
dc.contributor.author Čablová, Andrea
dc.contributor.author Rouchal, Michal
dc.contributor.author Hanulíková, Barbora
dc.contributor.author Vícha, Jan
dc.contributor.author Dastychová, Lenka
dc.contributor.author Prucková, Zdeňka
dc.contributor.author Vícha, Robert
dc.relation.ispartof Rapid Communications in Mass Spectrometry
dc.identifier.issn 0951-4198 OCLC, Ulrich, Sherpa/RoMEO, JCR
dc.date.issued 2017
utb.relation.volume 31
utb.relation.issue 18
dc.citation.spage 1510
dc.citation.epage 1518
dc.type article
dc.language.iso en
dc.publisher John Wiley and Sons Ltd.
dc.identifier.doi 10.1002/rcm.7919
dc.relation.uri http://onlinelibrary.wiley.com/doi/10.1002/rcm.7919/full
dc.description.abstract Rationale: Bisimidazolium salts (BIMs) represent an interesting family of ditopic ligands that are used in the construction of supramolecular systems with hosts based on cyclodextrins or cucurbit[n]urils. Understanding the fragmentation mechanism of individual BIMs and how this mechanism changes after complexation with cucurbit[n]urils can bring new insight into the intrinsic host-guest relationship, thereby allowing utilization of mass spectrometry to describe binding behavior. Methods: Selectively 2H-labeled bisimidazolium salts were prepared and fully characterized by spectroscopic methods. All MSn experiments were conducted in the positive-ion mode using an electrospray ionization (ESI) ion-trap mass spectrometer. The structures of the proposed fragments were supported by theoretical optimizations performed at the B3LYP/6-31G(d) level of density functional theory (DFT) using the Spartan'14 program. Results: Using selectively deuterium-labeled isotopologues of two adamantylated bisimidazolium salts and DFT calculations, we describe the fragmentation pathways of bisimidazolium salts. The release of two important adamantane moieties, [C11H17]+ and C11H16, from M2+ was determined, although the former was strongly preferred. In contrast, when M2+ was complexed with CB7, the neutral loss of the C11H16 fragment was favored. The fragmentation pattern strongly depended on the steric hindrance of the M2+ guest against slippage of the CB7 unit over the guest molecular axle. Conclusions: The structures of two adamantane-based fragments and the mechanisms of their formation were rationalized. Two distinct geometric arrangements for the adamantane cage inside the CB7 cavity were hypothesized to explain the differences in the fragmentation patterns for guests with minimal, moderate, and high steric hindrance. This finding brings new insight into the understanding of intrinsic behavior of the adamantane-based guests inside the CB7 cavity. Copyright © 2017 John Wiley & Sons, Ltd. en
utb.faculty Faculty of Technology
utb.faculty University Institute
dc.identifier.uri http://hdl.handle.net/10563/1007456
utb.identifier.obdid 43876532
utb.identifier.scopus 2-s2.0-85027303488
utb.identifier.wok 000407391400004
utb.identifier.coden RCMSE
utb.source j-scopus
dc.date.accessioned 2017-09-14T09:00:50Z
dc.date.available 2017-09-14T09:00:50Z
dc.description.sponsorship Internal Founding Agency of Tomas Bata University [IGA/FT/2017/001]; Ministry of Education, Youth and Sports of the Czech Republic, Program NPU I [LO1504]; Czech Science Foundation [16-05691S]
utb.ou Centre of Polymer Systems
utb.contributor.internalauthor Čablová, Andrea
utb.contributor.internalauthor Rouchal, Michal
utb.contributor.internalauthor Hanulíková, Barbora
utb.contributor.internalauthor Vícha, Jan
utb.contributor.internalauthor Dastychová, Lenka
utb.contributor.internalauthor Prucková, Zdeňka
utb.contributor.internalauthor Vícha, Robert
utb.wos.affiliation [Cablova, Andrea; Rouchal, Michal; Dastychova, Lenka; Pruckova, Zdenka; Vicha, Robert] Tomas Bata Univ Zlin, Fac Technol, Dept Chem, Vavreckova 275, Zlin 76001, Zlin, Czech Republic; [Hanulikova, Barbora; Vicha, Jan] Tomas Bata Univ Zlin, Ctr Polymer Syst, Tomase Bati 5678, Trida 76001, Zlin, Czech Republic
utb.scopus.affiliation Department of Chemistry, Faculty of Technology, Tomas Bata University in Zlín, Vavrečkova 275, Zlín, Czech Republic; Center of Polymer Systems, Tomas Bata University in Zlín, třída, Tomáše Bati 5678, Zlín, Czech Republic
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