Multifrequency Multiresonance EPR Investigation of Halogen-bonded Complexes Involving Neutral Nitroxide Radicals
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Thomas Lohmiller
Abstract
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 14N 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 14N 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. 19F 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.
Dedicated to: Kev Salikhov on the occasion of his 80th birthday.
Acknowledgement:
This work was supported by the Max-Planck-Gesellschaft and the Cluster of Excellence RESOLV (EXC 1069) funded by the Deutsche Forschungsgemeinschaft (DFG).
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©2017 Walter de Gruyter GmbH, Berlin/Boston
Articles in the same Issue
- Frontmatter
- Preface
- Basic and Combination Cross-Features in X- and Q-band HYSCORE of the 15N Labeled Bacteriochlorophyll a Cation Radical
- An EPR Study of Small Magnetic Nanoparticles
- Magnetic Resonance Study of the Spin-1/2 Quantum Magnet BaAg2Cu[VO4]2
- Triarylmethyl Radicals: An EPR Study of 13C Hyperfine Coupling Constants
- Natural Abundance Nitrogen-15 NMR in Thermotropic Liquid Crystals With Cyano-Group
- Surface Hydroxyl OH Defects of η-Al2O3 and χ-Al2O3 by Solid State NMR, XRD, and DFT Calculations
- THz ESR study of Spinel Compound GeCo2O4
- Self-Association of Glycyrrhizic Acid. NMR Study
- A Site-Specific Study of the Magnetic Field-Dependent Proton Spin Relaxation of an Iridium N-Heterocyclic Carbene Complex
- Multifrequency Multiresonance EPR Investigation of Halogen-bonded Complexes Involving Neutral Nitroxide Radicals
- Electron Paramagnetic Resonance and DFT Analysis of the Effects of Bulky Perfluoroalkyl Substituents on a Vanadyl Perfluoro Phthalocyanine
- Coordination of the Mn4+-Center in Layered Li[Co0.98Mn0.02]O2 Cathode Materials for Lithium-Ion Batteries
- Triarylmethyl Radical: EPR Signal to Noise at Frequencies between 250 MHz and 1.5 GHz and Dependence of Relaxation on Radical and Salt Concentration and on Frequency
Articles in the same Issue
- Frontmatter
- Preface
- Basic and Combination Cross-Features in X- and Q-band HYSCORE of the 15N Labeled Bacteriochlorophyll a Cation Radical
- An EPR Study of Small Magnetic Nanoparticles
- Magnetic Resonance Study of the Spin-1/2 Quantum Magnet BaAg2Cu[VO4]2
- Triarylmethyl Radicals: An EPR Study of 13C Hyperfine Coupling Constants
- Natural Abundance Nitrogen-15 NMR in Thermotropic Liquid Crystals With Cyano-Group
- Surface Hydroxyl OH Defects of η-Al2O3 and χ-Al2O3 by Solid State NMR, XRD, and DFT Calculations
- THz ESR study of Spinel Compound GeCo2O4
- Self-Association of Glycyrrhizic Acid. NMR Study
- A Site-Specific Study of the Magnetic Field-Dependent Proton Spin Relaxation of an Iridium N-Heterocyclic Carbene Complex
- Multifrequency Multiresonance EPR Investigation of Halogen-bonded Complexes Involving Neutral Nitroxide Radicals
- Electron Paramagnetic Resonance and DFT Analysis of the Effects of Bulky Perfluoroalkyl Substituents on a Vanadyl Perfluoro Phthalocyanine
- Coordination of the Mn4+-Center in Layered Li[Co0.98Mn0.02]O2 Cathode Materials for Lithium-Ion Batteries
- Triarylmethyl Radical: EPR Signal to Noise at Frequencies between 250 MHz and 1.5 GHz and Dependence of Relaxation on Radical and Salt Concentration and on Frequency
