Pulsed EPR Dipolar Spectroscopy on Spin Pairs with one Highly Anisotropic Spin Center: The Low-Spin FeIII Case

Chemistry : a European Journal
Dinar AbdullinOlav Schiemann

Abstract

Pulsed electron paramagnetic resonance (EPR) dipolar spectroscopy (PDS) offers several methods for measuring dipolar coupling constants and thus the distance between electron spin centers. Up to now, PDS measurements have been mostly applied to spin centers whose g-anisotropies are moderate and therefore have a negligible effect on the dipolar coupling constants. In contrast, spin centers with large g-anisotropy yield dipolar coupling constants that depend on the g-values. In this case, the usual methods of extracting distances from the raw PDS data cannot be applied. Here, the effect of the g-anisotropy on PDS data is studied in detail on the example of the low-spin Fe3+ ion. First, this effect is described theoretically, using the work of Bedilo and Maryasov (Appl. Magn. Reson. 2006, 30, 683-702) as a basis. Then, two known Fe3+ /nitroxide compounds and one new Fe3+ /trityl compound were synthesized and PDS measurements were carried out on them using a method called relaxation induced dipolar modulation enhancement (RIDME). Based on the theoretical results, a RIDME data analysis procedure was developed, which facilitated the extraction of the inter-spin distance and the orientation of the inter-spin vector relative to the Fe3...Continue Reading

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Citations

Jan 9, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Dinar Abdullin, Olav Schiemann
Jan 7, 2021·Chemistry : a European Journal·Nico FleckOlav Schiemann
May 14, 2021·The Journal of Physical Chemistry. B·Zikri HasanbasriSunil Saxena

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Methods Mentioned

BETA
column chromatography

Software Mentioned

mtsslWizard
PeldorFit
DeerAnalysis
TRAVIS
xtb
PELDOR
RIDME
MtssWizard
MD
DipFit

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