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          Institute: MPI für bioanorganische Chemie     Collection: MPI für bioanorganische Chemie     Display Documents

ID: 733896.0, MPI für bioanorganische Chemie / MPI für bioanorganische Chemie
Multifrequency Multiresonance EPR Investigation of Halogen-bonded Complexes Involving Neutral Nitroxide Radicals
Authors:Lohmiller, Thomas; Vibhute, Mahesh A.; Lubitz, Wolfgang; Savitsky, Anton
Date of Publication (YYYY-MM-DD):2017
Title of Journal:Zeitschrift fur Physikalische Chemie-International Journal of Research in Physical Chemistry & Chemical Physics
Journal Abbrev.:Z.Phys.Chem.
Issue / Number:4 Sp. Iss. SI
Start Page:867
End Page:886
Review Status:Internal review
Audience:Experts Only
Abstract / Description:Halogen-bonded complexes with neutral nitroxide radicals as the Lewis base have been investigated in liquid and frozen solutions by multifrequency CW and pulse EPR spectroscopies, including ENDOR and ELDOR-detected NMR (EDNMR) techniques. The non-covalent interaction with iodopentafluorobenzene as halogen-bond donor is shown to affect a variety of EPR parameters of the stable nitroxide radicals. In liquid solution, only bulk effects on the EPR signal, i.e. isotropic g value, isotropic N-14 hyperfine coupling and linewidth, are observed. Experiments on frozen solutions allow for a more in-depth dissection of complexing effects. W-band EPR spectra at cryogenic temperatures exhibit multiple signal components of different N-14 hyperfine interactions and spectral widths. This demonstrates the coexistence of several halogen-bonded complexes that differ in donor-acceptor binding geometries. These complexes have different relaxation properties, which allow for their spectral discrimination. F-19 ENDOR experiments prove the origin of these effects to be different specific intermolecular interactions rather than a consequence of changes in the solvation environment. The EPR spectra yet reveal a strong influence of solvent composition on the amount of the various complexes formed. The introduced methodology for the characterization of such adducts improves our understanding of halogen bonding and could be helpful in the development of tailor-made donors and complexes for specific applications.
Comment of the Author/Creator:Date: 2017, APR 2017
External Publication Status:published
Document Type:Article
Version Comment:Automatic journal name synchronization
Communicated by:N. N.
Affiliations:MPI für bioanorganische Chemie
Identifiers:ISI:000394164200011 [ID No:1]
ISSN:0942-9352 [ID No:2]
DOI:10.1515/zpch-2016-0870 [ID No:3]
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