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Simultaneous Introduction of Two Nitroxides in the Reaction: A New Approach to the Synthesis of Heterospin Complexes Full article

Journal Inorganic Chemistry
ISSN: 0020-1669
Output data Year: 2017, Volume: 56, Number: 23, Pages: 14567-14576 Pages count : 10 DOI: 10.1021/acs.inorgchem.7b02308
Authors Ovcharenko Victor 1 , Kuznetsova Olga 1 , Fursova Elena 1 , Letyagin Gleb 1 , Romanenko Galina 1 , Bogomyakov Artem 1 , Zueva Ekaterina 2
Affiliations
1 International Tomography Center, Institutskaya Street 3a, Novosibirsk 630090, Russian Federation
2 Kazan National Research Technological University, 68 K. Marx Street, Kazan 420015, Russian Federation

Abstract: A new approach to the synthesis of multispin compounds has been developed, namely, the simultaneous introduction of two dif ferent stable nitroxides (nitronyl nitroxide and imino nitroxide) in a reaction with a metal ion. An important characteristic of the new method is that nitronyl nitroxide and imino nitroxide introduced in the reaction with the metal are the products of different series; i.e., the nitronyl nitroxide molecule differs from the imino nitroxide molecule not only in one additional oxygen molecule per molecule but also in another substituent in the side chain of the organic paramagnet. This possibility was demonstrated on the synthesis of multispin compounds [Ni2(A1)(L2)2(Piv)(MeOH)], [Ni2(L1)(A2)2(Piv)(H2O)], [Co2(A1)(L2)2(Piv)(MeOH)], and [Co3(L1)2(A2)2(Piv)2], in which Ln and An differ in the substituent in the phenyl ring. The number of multispin compounds that can be synthesized by the proposed method is almost unlimited. The heterospin complexes of transition metals with coordinated nitronyl nitroxide and imino nitroxide in one molecule contain energy-different exchange interaction channels that differ in both magnitude and sign, as confirmed by the quantum-chemical analysis of exchange channels in [Ni(B1)(B2)2](NO3)2. The series of mixed-radical complexes may include compounds with nontrivial magnetic properties such as [Co2(A1)(L2)2(Piv)(MeOH)], which experiences bulk magnetic ordering below 3.5 K.
Cite: Ovcharenko V. , Kuznetsova O. , Fursova E. , Letyagin G. , Romanenko G. , Bogomyakov A. , Zueva E.
Simultaneous Introduction of Two Nitroxides in the Reaction: A New Approach to the Synthesis of Heterospin Complexes
Inorganic Chemistry. 2017. V.56. N23. P.14567-14576. DOI: 10.1021/acs.inorgchem.7b02308 WOS Scopus
Dates:
Submitted: Sep 7, 2017
Published print: Dec 4, 2017
Identifiers:
Web of science: WOS:000417342200020
Scopus: 2-s2.0-85037605767
Citing:
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Scopus 16
Web of science 16
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