Abstract
In this work, we report on a detailed high-field EPR investigation of magnetic parameters of deuterated nitroxide radicals dissolved in deuterated frozen solvents of polar or unpolar, protic or aprotic character including ortho-terphenyl, methanol, propanol, glycerol, aniline, phenol, and water. The analysis of the high-resolution W-band (95 GHz) pulsed ELDOR-detected NMR (EDNMR) and 244 GHz cw EPR spectra yielded precise electron Zeeman, gxx, 14N hyperfine, Azz, and 14N quadrupole, Pzz, tensor components, which are most sensitive probes for the microenvironment of dissolved nitroxide radicals. Remarkable changes in the solvation networks were found in the various matrices. The solvent-dependent magnetic parameters of the nitroxide are discussed on the basis of previous semi-empirical and DFT quantum chemical calculations in an attempt to adequately model the nitroxide–matrix interactions. The obtained results demonstrate that the principal values of all the magnetic interaction parameters primarily depend on the nitroxide hydrogen-bond situation and the type of hydrogen-bond donor group of the solvent. The solvent bulk polarity, as described by the static dielectric constant, is of minor importance.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
