Abstract
We examine the electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopy of three quite distinct high-spin Mn(II) systems and describe experimental techniques and methods of analysis that are useful in their study. We demonstrate that this S = 5/2 metal center provides useful orientation-selection through the Zero-Field Splitting (ZFS) tensor that enables determination of a 13C hyperfine-coupling tensor with extremely small hyperfine interaction. We also demonstrate that Mims suppression effects can be used in concert with orientation-selection to edit complex [1,2]H ENDOR patterns that can be produced by even a ‘simple’ center with a single Mn(II). We develop a perturbation-based approach to understanding second-order shifts in Mn(II) ENDOR responses that occur in systems with intermediate ZFS values, and show that these shifts can be used to estimate the values of the ZFS tensors.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 969-986 |
| Number of pages | 18 |
| Journal | Applied Magnetic Resonance |
| Volume | 55 |
| Issue number | 9 |
| DOIs | |
| State | Published - Sep 2024 |
Funding
This work was supported by the NIH (GM111097) and NSF (CHE2333907). We gratefully acknowledge the collaborators and their coworkers whose remarkable chemistry and biochemistry we had the good fortune to integrate with: (alphabetically) Judith P. Klinman; Alex McSkimming; Adam R. Offenbacher.
ASJC Scopus subject areas
- Atomic and Molecular Physics, and Optics