Platform for High-Spin Molecules: A Verdazyl-Nitronyl Nitroxide Triradical with Quartet Ground State; Journal of the American Chemical Society (JACS); Vol. 143, iss. 21

Bibliografiske detaljer
Parent link:	Journal of the American Chemical Society (JACS) Vol. 143, iss. 21.— 2021.— [P. 8164–8176]
Institution som forfatter:	Национальный исследовательский Томский политехнический университет Исследовательская школа химических и биомедицинских технологий
Andre forfattere:	Tretjyakov E. V. Evgeny Viktorovich, Petunin P. V. Pavel Vasilievich, Zhivetjeva S. I. Svetlana Ivanovna, Gorbunov D. E. Dmitry Evgenjevich, Gritsan N. P. Nina Petrovna, Fedin M. V. Matvey Vladimirovich, Stas D. V. Dmitry Vladimirovich, Samoylova R. I. Rimma Ivanovna, Bagryanskaya I. Yu. Irina Yurjevna, Shundrina I. K. Inna Kazimirovna, Bogomyakov A. S. Artem Stepanovich, Kazantsev M. S. Maksim Sergeevich, Postnikov P. S. Pavel Sergeevich, Trusova M. E. Marina Evgenievna, Ovcharenko V. I. Viktor Ivanovich
Summary:	Title screen Thermally resistant air-stable organic triradicals with a quartet ground state and a large energy gap between spin states are still unique compounds. In this work, we succeeded to design and prepare the first highly stable triradical, consisting of oxoverdazyl and nitronyl nitroxide radical fragments, with a quartet ground state. The triradical and its diradical precursor were synthesized via a palladium-catalyzed cross-coupling reaction of diiodoverdazyl with nitronyl nitroxide-2-ide gold(I) complex. Both paramagnetic compounds were fully characterized by single-crystal X-ray diffraction analysis, superconducting quantum interference device magnetometry, EPR spectroscopy in various matrices, and cyclic voltammetry. In the diradical, the verdazyl and nitronyl nitroxide centers demonstrated full reversibility of redox process, while for the triradical, the electrochemical reduction and oxidation proceed at practically the same redox potentials, but become quasi-reversible. A series of high-level CASSCF/NEVPT2 calculations was performed to predict inter- and intramolecular exchange interactions in crystals of di- and triradicals and to establish their magnetic motifs. Based on the predicted magnetic motifs, the temperature dependences of the magnetic susceptibility were analyzed, and the singlet-triplet (135±10 cm-1) and doublet-quartet (17±2 and 152±19 cm-1) splitting was found to be moderate. Unique high stability of synthesized verdazyl-nitronylnitroxide triradical opens new perspectives for further functionalization and design of high-spin systems with four or more spins. Режим доступа: по договору с организацией-держателем ресурса
Sprog:	engelsk
Udgivet:	2021
Fag:	электронный ресурс труды учёных ТПУ высокоспиновые молекулы монокристаллы парамагнитные соединения бирадикалы обменные взаимодействия температурные зависимости
Online adgang:	https://pubs.acs.org/doi/10.1021/jacs.1c02938?goto=supporting-info
Format:	Electronisk Book Chapter
KOHA link:	https://koha.lib.tpu.ru/cgi-bin/koha/opac-detail.pl?biblionumber=666286