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Vanadyl Porphyrin Complex Functionalized with Nitronyl Nitroxide Full article

Journal Inorganic Chemistry
ISSN: 0020-1669 , E-ISSN: 1520-510X
Output data Year: 2026, Volume: 65, Number: 29, Pages: 16749–16762 Pages count : DOI: 10.1021/acs.inorgchem.6c01368
Authors Zimina Anastasiya M. 1 , Shmakov Alexandr S. 2,3 , Stepanov Andrey V. 1 , Lisyukova Anastasia 1 , Zayakin Igor A. 1 , Sosunov Egor A. 4 , Gritsan Nina P. 5 , Dmitriev Alexey A. 5 , Akimov Aleksander V. 2 , Tretyakov Evgeny V. 1
Affiliations
1 N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Ave. 47, 119991 Moscow, Russian Federation
2 Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences, golovka, 142432 Moscow, Russian Federation
3 Faculty of Fundamental Physical and Chemical Engineering, Lomonosov Moscow State University, 119991 Moscow, Russian Federation
4 N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky Ave. 31, 119991 Moscow, Russian Federation
5 V. V. Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences, Institutskaya 3, 630090 Novosibirsk, Russian Federation

Abstract: The development of effective frameworks for coupling chemically synthesized qubits is essential for advancing molecular quantum technologies. Vanadium(IV) (VO) magnetic centers are promising candidates for molecular quantum units. To create a novel type of two-qubit vanadyl-containing system, we synthesized and fully characterized the first vanadyl porphyrin derivative featuring a conjugated nitronyl nitroxide radical (VO(Por)–NN). Using X-ray diffraction (XRD), we determined the molecular and crystal structures of the solvate complex, VO(Por)–NN·n(CH2Cl2). When dissolved in dichloromethane, this solvate complex produces an electron paramagnetic resonance (EPR) spectrum that is a superposition of two distinct signals: the spectrum of the monomeric VO(Por)–NN complex, in which the paramagnetic centers (vanadyl and nitronyl nitroxide) do not interact; and the spectrum of the dimeric {VO(Por)–NN}2 species, in which exchange interactions between the spins are observed. Desolvation of a polycrystalline sample triggers its complete conversion into the dimeric form {VO(Por)–NN}2, thereby activating exchange interactions between the vanadyl and nitroxide spins. To the best of our knowledge, such self-organization of spin systems involving a vanadyl center and an organic radical has not been observed previously. It represents a novel supramolecular approach to the construction of multispin clusters.
Cite: Zimina A.M. , Shmakov A.S. , Stepanov A.V. , Lisyukova A. , Zayakin I.A. , Sosunov E.A. , Gritsan N.P. , Dmitriev A.A. , Akimov A.V. , Tretyakov E.V.
Vanadyl Porphyrin Complex Functionalized with Nitronyl Nitroxide
Inorganic Chemistry. 2026. V.65. N29. P.16749–16762. DOI: 10.1021/acs.inorgchem.6c01368 WOS OpenAlex
Dates:
Submitted: Mar 14, 2026
Published online: Jul 27, 2026
Identifiers:
≡ Web of science: WOS:001820080500001
≡ OpenAlex: W7168299569
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