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

Bibliographic Details
Parent link:The Journal of Physical Chemistry A.— .— Washington: ACS Publications
Vol. 129, iss. 7.— 2025.— P. 1808-1816
Other Authors: 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
Summary: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
Published: 2025
Subjects:
Online Access:https://doi.org/10.1021/acs.jpca.4c06823
Format: Electronic Book Chapter
KOHA link:https://koha.lib.tpu.ru/cgi-bin/koha/opac-detail.pl?biblionumber=679747