The Ground State of Multispin Systems Based on Verdazyl and Nitrene Radicals: An EPR and Quantum-Chemical Study

The Ground State of Multispin Systems Based on Verdazyl and Nitrene Radicals: An EPR and Quantum-Chemical Study Full article

Journal

Journal of Physical Chemistry A
ISSN: 1089-5639 , E-ISSN: 1520-5215

Output data

Year: 2025, Volume: 129, Number: 7, Pages: 1808–1816 Pages count : DOI: 10.1021/acs.jpca.4c06823

Authors

Shmakov Alexandr S. ¹ , Shurikov Matvey K. ² , Korchagin Denis V. ¹ , Votkina Darya E. ² , Postnikov Pavel S. ² , Akimov Aleksander V. ¹ , Petunin Pavel V. ² , Tretyakov Evgeny V. ³

Affiliations

1	Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry of the Russian Academy of Sciences, Academician Semenov Ave. 1, Chernogolovka 142432, Russian Federation
2	Research School of Chemistry & Applied Biomedical Sciences, Tomsk Polytechnic University, Lenin Ave. 30, Tomsk 634050, Russian Federation
3	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Ave. 47, Moscow 119991, Russian Federation

In this study, low-temperature EPR spectroscopy and quantum-chemical techniques were employed to investigate multispin systems─1,5-diphenyl-3-(3-nitrenophenyl)-6-oxoverdazyl and 1,5-diphenyl-3-(4-nitrenophenyl)-6-oxoverdazyl─that contain a nitrene center at either a meta- or para-position, respectively. Ground states and magnetic zero-field splitting (ZFS) parameters of these multispin systems were determined by experimental and computational methods. The results indicated that the high-spin quartet state is a ground state, and the quartet–doublet energy gap is close to 10 kcal/mol for the para-position of the nitrene group, with ZFS parameters D = 0.292 cm–1 and E/D = 0.002 cm–1. In contrast, for the meta-position, the low-spin doublet state is favored with an energy gap of 1 kcal/mol. The observed difference in the ground states could be qualitatively explained by an analysis of the spin density distribution and by delocalization of the unpaired π-electron of the nitrene center. Overall, this study provides valuable insights into the electronic structures and magnetic parameters of such multispin systems.

Shmakov A.S. , Shurikov M.K. , Korchagin D.V. , Votkina D.E. , Postnikov P.S. , Akimov A.V. , Petunin P.V. , Tretyakov E.V.
The Ground State of Multispin Systems Based on Verdazyl and Nitrene Radicals: An EPR and Quantum-Chemical Study
Journal of Physical Chemistry A. 2025. V.129. N7. P.1808–1816. DOI: 10.1021/acs.jpca.4c06823 WOS OpenAlex

Web of science:	WOS:001387043300001
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