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X-Band Parallel-Mode and Multifrequency Electron Paramagnetic Resonance Spectroscopy of S = 1/2 Bismuth Centers
[Image: see text] The recent successes in the isolation and characterization of several bismuth radicals inspire the development of new spectroscopic approaches for the in-depth analysis of their electronic structure. Electron paramagnetic resonance (EPR) spectroscopy is a powerful tool for the char...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2022
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9326968/ https://www.ncbi.nlm.nih.gov/pubmed/35834368 http://dx.doi.org/10.1021/acs.inorgchem.2c01141 |
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author | Haak, Julia Krüger, Julia Abrosimov, Nikolay V. Helling, Christoph Schulz, Stephan Cutsail III, George E. |
author_facet | Haak, Julia Krüger, Julia Abrosimov, Nikolay V. Helling, Christoph Schulz, Stephan Cutsail III, George E. |
author_sort | Haak, Julia |
collection | PubMed |
description | [Image: see text] The recent successes in the isolation and characterization of several bismuth radicals inspire the development of new spectroscopic approaches for the in-depth analysis of their electronic structure. Electron paramagnetic resonance (EPR) spectroscopy is a powerful tool for the characterization of main group radicals. However, the large electron–nuclear hyperfine interactions of Bi ((209)Bi, I = 9/2) have presented difficult challenges to fully interpret the spectral properties for some of these radicals. Parallel-mode EPR (B(1)∥B(0)) is almost exclusively employed for the study of S > 1/2 systems but becomes feasible for S = 1/2 systems with large hyperfine couplings, offering a distinct EPR spectroscopic approach. Herein, we demonstrate the application of conventional X-band parallel-mode EPR for S = 1/2, I = 9/2 spin systems: Bi-doped crystalline silicon (Si:Bi) and the molecular Bi radicals [L(X)Ga](2)Bi(•) (X = Cl or I) and [L(Cl)GaBi((Me)cAAC)](•+) (L = HC[MeCN(2,6-iPr(2)C(6)H(3))](2)). In combination with multifrequency perpendicular-mode EPR (X-, Q-, and W-band frequencies), we were able to fully refine both the anisotropic g- and A-tensors of these molecular radicals. The parallel-mode EPR experiments demonstrated and discussed here have the potential to enable the characterization of other S = 1/2 systems with large hyperfine couplings, which is often challenging by conventional perpendicular-mode EPR techniques. Considerations pertaining to the choice of microwave frequency are discussed for relevant spin-systems. |
format | Online Article Text |
id | pubmed-9326968 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-93269682022-07-28 X-Band Parallel-Mode and Multifrequency Electron Paramagnetic Resonance Spectroscopy of S = 1/2 Bismuth Centers Haak, Julia Krüger, Julia Abrosimov, Nikolay V. Helling, Christoph Schulz, Stephan Cutsail III, George E. Inorg Chem [Image: see text] The recent successes in the isolation and characterization of several bismuth radicals inspire the development of new spectroscopic approaches for the in-depth analysis of their electronic structure. Electron paramagnetic resonance (EPR) spectroscopy is a powerful tool for the characterization of main group radicals. However, the large electron–nuclear hyperfine interactions of Bi ((209)Bi, I = 9/2) have presented difficult challenges to fully interpret the spectral properties for some of these radicals. Parallel-mode EPR (B(1)∥B(0)) is almost exclusively employed for the study of S > 1/2 systems but becomes feasible for S = 1/2 systems with large hyperfine couplings, offering a distinct EPR spectroscopic approach. Herein, we demonstrate the application of conventional X-band parallel-mode EPR for S = 1/2, I = 9/2 spin systems: Bi-doped crystalline silicon (Si:Bi) and the molecular Bi radicals [L(X)Ga](2)Bi(•) (X = Cl or I) and [L(Cl)GaBi((Me)cAAC)](•+) (L = HC[MeCN(2,6-iPr(2)C(6)H(3))](2)). In combination with multifrequency perpendicular-mode EPR (X-, Q-, and W-band frequencies), we were able to fully refine both the anisotropic g- and A-tensors of these molecular radicals. The parallel-mode EPR experiments demonstrated and discussed here have the potential to enable the characterization of other S = 1/2 systems with large hyperfine couplings, which is often challenging by conventional perpendicular-mode EPR techniques. Considerations pertaining to the choice of microwave frequency are discussed for relevant spin-systems. American Chemical Society 2022-07-14 2022-07-25 /pmc/articles/PMC9326968/ /pubmed/35834368 http://dx.doi.org/10.1021/acs.inorgchem.2c01141 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Haak, Julia Krüger, Julia Abrosimov, Nikolay V. Helling, Christoph Schulz, Stephan Cutsail III, George E. X-Band Parallel-Mode and Multifrequency Electron Paramagnetic Resonance Spectroscopy of S = 1/2 Bismuth Centers |
title | X-Band
Parallel-Mode and Multifrequency Electron
Paramagnetic Resonance Spectroscopy of S = 1/2 Bismuth
Centers |
title_full | X-Band
Parallel-Mode and Multifrequency Electron
Paramagnetic Resonance Spectroscopy of S = 1/2 Bismuth
Centers |
title_fullStr | X-Band
Parallel-Mode and Multifrequency Electron
Paramagnetic Resonance Spectroscopy of S = 1/2 Bismuth
Centers |
title_full_unstemmed | X-Band
Parallel-Mode and Multifrequency Electron
Paramagnetic Resonance Spectroscopy of S = 1/2 Bismuth
Centers |
title_short | X-Band
Parallel-Mode and Multifrequency Electron
Paramagnetic Resonance Spectroscopy of S = 1/2 Bismuth
Centers |
title_sort | x-band
parallel-mode and multifrequency electron
paramagnetic resonance spectroscopy of s = 1/2 bismuth
centers |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9326968/ https://www.ncbi.nlm.nih.gov/pubmed/35834368 http://dx.doi.org/10.1021/acs.inorgchem.2c01141 |
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