Abstract
The zero-field splitting parameter D of the localized cyclopentane-1,3-diyl triplet diradicals T, generated in a 2-methyltetrahydrofuran (MTHF) glass matrix at 77 K through photochemical deazetation of the corresponding azoalkanes 1-13, has been determined by EPR spectroscopy. It is demonstrated that the D parameter reliably reflects the changes caused by the alkyl (simple and oxyfunctionalized), vinyl, and carbonyl substituents of the spin densities at the radical site. Thus, spin delocalization of the substituents and stabilization of the radical center follow the order vinyl > phenyl > carbonyl >> alkyl. This trend is confirmed by the excellent linear correlations with the reported alpha-hyperfine coupling constants (alpha-hfc) of the corresponding monoradicals and computed semiempirical (PM3 method) spin densities of the radical fragments M.
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.
