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Updated: Oct 25, 2025

Paramagnetic Relaxation Enhancement for Detecting and Characterizing Self-Associations of Intrinsically Disordered Proteins
Published on: September 23, 2021
Observability of Paramagnetic NMR Signals at over 10 000 ppm Chemical Shifts
Jonas C Ott1, Elizaveta A Suturina2, Ilya Kuprov3
1Anorganisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 276, 69120, Heidelberg, Germany.
Abstract:
We report an experimental observation of 31 P NMR resonances shifted by over 10 000 ppm (meaning percent range, and a new record for solutions), and similar 1 H chemical shifts, in an intermediate-spin square planar ferrous complex [tBu (PNP)Fe-H], where PNP is a carbazole-based pincer ligand. Using a combination of electronic structure theory, nuclear magnetic resonance, magnetometry, and terahertz electron paramagnetic resonance, the influence of magnetic anisotropy and zero-field splitting on the paramagnetic shift and relaxation enhancement is investigated. Detailed spin dynamics simulations indicate that, even with relatively slow electron spin relaxation (T1 ≈10-11 s), it remains possible to observe NMR signals of directly metal-bonded atoms because pronounced rhombicity in the electron zero-field splitting reduces nuclear paramagnetic relaxation enhancement.
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