W-band EPR studies of high-spin nitrenes with large spin-orbit contribution to zero-field splitting

The Journal of Chemical Physics
Alexander AkimovAnton Savitsky

Abstract

First W-band 94 GHz EPR spectra of randomly oriented triplet, quintet, and septet nitrenes formed during the photolysis of 1,3,5-triazido-2,4,6-tribromobenzene in cryogenic matrices are reported. In comparison with conventional X-band 9 GHz electron paramagnetic resonance (EPR) spectroscopy, W-band EPR spectroscopy allows the detection and complete spectroscopic characterization of all paramagnetic species formed at different stages of the photolysis of aromatic polyazides. This type of spectroscopy is of paramount importance for experimental determination of the sign of the zero-field splitting (ZFS) parameters of high-spin molecules with large spin-orbit contribution to the ZFS, caused by the effect of heavy atoms. The study shows that triplet 1,3-diazido-2,4,6-tribromo-5-nitrenobenzene (T1) has DT = 1.369 cm(-1), ET = 0.093 cm(-1), and g = 2.0033, quintet 1-azido-2,4,6-tribromo-3,5-dinitrenobenzene (Q1) shows DQ = - 0.306 cm(-1), EQ = 0.0137 cm(-1), and g = 2.0070, and septet 2,4,6-tribromo-1,3,5-trinitrenobenzene (S1) has DS = - 0.203 cm(-1), ES = 0, and g = 2.0073. The experimental ZFS parameters agree well with the results of density functional theory calculations at the PBE/Ahlrichs-DZ level of theory, showing that such ...Continue Reading

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Citations

Oct 28, 2015·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Sergei V Chapyshev
May 12, 2017·Angewandte Chemie·Alexander V AkimovEugenii Y Misochko
May 29, 2018·Angewandte Chemie·Curt Wentrup
Jul 3, 2019·Angewandte Chemie·Enrique Mendez-VegaWolfram Sander
Jun 25, 2020·Chemistry : a European Journal·Sergei V ChapyshevWolfram Sander
Oct 26, 2018·The Journal of Physical Chemistry. a·Denis V KorchaginEugenii Ya Misochko

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