В престижном журнала The Journal of the American Chemical Society (JACS) (IF 15,419) опубликована статья с участием сотрудников Института д.х.н. И.Ю. Багрянской (внс, рук. группы ГРСА), к.х.н. И.К. Шундриной (снс, ЛМР, рук. группы ГТ) и к.х.н. М.C. Казанцева (завлаб ЛОЭ):
Platform for High-Spin Molecules: A Verdazyl-Nitronyl Nitroxide Triradical with Quartet Ground State
Получен и структурно охарактеризован гетероспиновый квартетный трирадикал, содержащий оксовердазил и два нитронилнитроксильных фрагмента. Трирадикал устойчив на воздухе и обладает высокой термической стабильностью в инертной атмосфере. Данные магнитных измерений указывают на достаточно сильные внутримолекулярные обменные ферромагнитные взаимодействия между парамагнитными центрами. Полученный гетероспиновый трирадикал с квартетным основным состоянием может служить платформой для получения дендримерных высокоспиновых систем.
Abstract
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.
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