The Ground State of Multispin Systems Based on Verdazyl and Nitrene Radicals: An EPR and Quantum-Chemical Study; The Journal of Physical Chemistry A; Vol. 129, iss. 7

Detalles Bibliográficos
Parent link:The Journal of Physical Chemistry A.— .— Washington: ACS Publications
Vol. 129, iss. 7.— 2025.— P. 1808-1816
Otros Autores: Shmakov A. S. Alexandr, Shurikov M. K. Matvey Konstantinovich, Korchagin D. V. Denis, Votkina D. E. Darjya Evgenjevna, Postnikov P. S. Pavel Sergeevich, Akimov A. V. Aleksander, Petunin P. V. Pavel Vasilievich, Tretyakov E. V. Evgeny
Sumario:Title screen
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
Текстовый файл
AM_Agreement
Lenguaje:inglés
Publicado: 2025
Materias:
Acceso en línea:https://doi.org/10.1021/acs.jpca.4c06823
Formato: Electrónico Capítulo de libro
KOHA link:https://koha.lib.tpu.ru/cgi-bin/koha/opac-detail.pl?biblionumber=679747

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200 1 |a The Ground State of Multispin Systems Based on Verdazyl and Nitrene Radicals: An EPR and Quantum-Chemical Study  |f Alexandr S. Shmakov, Matvey K. Shurikov, Denis V. Korchagin [et al.] 
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330 |a 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 
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461 1 |t The Journal of Physical Chemistry A  |c Washington  |n ACS Publications 
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701 1 |a Shmakov  |b A. S.  |g Alexandr 
701 1 |a Shurikov  |b M. K.  |c Chemist  |c Laboratory assistant of Tomsk Polytechnic University  |f 2000-  |g Matvey Konstantinovich  |9 22267 
701 1 |a Korchagin  |b D. V.  |g Denis 
701 1 |a Votkina  |b D. E.  |c chemical engineer  |c Associate Scientist of the Tomsk Polytechnic University  |f 1995-  |g Darjya Evgenjevna  |9 21944 
701 1 |a Postnikov  |b P. S.  |c organic chemist  |c Associate Professor of Tomsk Polytechnic University, Candidate of chemical sciences  |f 1984-  |g Pavel Sergeevich  |9 15465 
701 1 |a Akimov  |b A. V.  |g Aleksander 
701 1 |a Petunin  |b P. V.  |c chemist  |c Associate Professor of Tomsk Polytechnic University, Candidate of Chemical Sciences  |f 1982-  |g Pavel Vasilievich  |9 19933 
701 1 |a Tretyakov  |b E. V.  |g Evgeny 
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