TY - JOUR

T1 - Ferromagnetically Coupled S=1 Chains in Crystals of Verdazyl-Nitronyl Nitroxide Diradicals

AU - Tretyakov, Evgeny V.

AU - Zhivetyeva, Svetlana I.

AU - Kazantsev, Maxim S.

AU - Shundrina, Inna K.

AU - Zaytseva, Elena V.

AU - Parkhomenko, Dmitriy A.

AU - Bagryanskaya, Elena G.

AU - Gorbunov, Dmitry E.

AU - Bagryanskaya, Irina Yu

AU - Petunin, Pavel V.

AU - Postnikov, Pavel S.

AU - Trusova, Marina E.

AU - Gritsan, Nina P.

AU - Bogomyakov, Artem S.

AU - Ovcharenko, Victor I.

AU - Postnikov, Pavel S.

N1 - Funding Information: This research was supported by the Ministry of Science and Higher Education of the Russian Federation (State Project „Science“ No. FSWW-2020-0011) and the Russian Science Foundation (grant No. 18-13-00173, synthesis and characterization). A.S.B. and V.I.O. are thankful to the Russian Science Foundation (grant No. 18-13-00380, magnetochemistry). D.E.G. and N.P.G. acknowledge support of the Ministry of Science and Higher Education of the Russian Federation (project No. 0304-2017-0008) and the Irkutsk Supercomputer Centre of the Siberian Branch of the Russian Academy of Sciences for computational resources. The authors would like to acknowledge the Multi-Access Chemical Research Center SB RAS for spectral and analytical measurements. Publisher Copyright: © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

PY - 2020

Y1 - 2020

N2 - Thermally stable organic diradicals with a triplet ground state along with large singlet-triplet energy gap have significant potential for advanced technological applications. A series of phenylene-bridged diradicals with oxoverdazyl and nitronyl nitroxide units were synthesized via a palladiumcatalyzed cross-coupling reaction of iodoverdazyls with a nitronyl nitroxide-2-ide gold(I) complex with high yields. The diradicals exhibit high stability and do not decompose in an inert atmosphere up to 180°C. For the diradicals, both substantial AF (∆EST≈-64 cm-1) and FM (∆EST≥ 25 and 100 cm-1) intramolecular exchange interactions were observed. The sign of the exchange interaction is determined both by the bridging moiety (para- or meta-phenylene) and by the type of oxoverdazyl block (C-linked or N-linked). Upon crystallization, diradicals with the triplet ground state form unique onedimensional exchange-coupled chains with strong intra- and weak inter-diradical ferromagnetic coupling.

AB - Thermally stable organic diradicals with a triplet ground state along with large singlet-triplet energy gap have significant potential for advanced technological applications. A series of phenylene-bridged diradicals with oxoverdazyl and nitronyl nitroxide units were synthesized via a palladiumcatalyzed cross-coupling reaction of iodoverdazyls with a nitronyl nitroxide-2-ide gold(I) complex with high yields. The diradicals exhibit high stability and do not decompose in an inert atmosphere up to 180°C. For the diradicals, both substantial AF (∆EST≈-64 cm-1) and FM (∆EST≥ 25 and 100 cm-1) intramolecular exchange interactions were observed. The sign of the exchange interaction is determined both by the bridging moiety (para- or meta-phenylene) and by the type of oxoverdazyl block (C-linked or N-linked). Upon crystallization, diradicals with the triplet ground state form unique onedimensional exchange-coupled chains with strong intra- and weak inter-diradical ferromagnetic coupling.

KW - ferromagnetically coupled chain

KW - high-spin molecules

KW - nitroxides

KW - triplet diradicals

KW - verdazyl radicals

UR - http://www.scopus.com/inward/record.url?scp=85136211221&partnerID=8YFLogxK

U2 - 10.1002/ANGE.202010041

DO - 10.1002/ANGE.202010041

M3 - Article

AN - SCOPUS:85136211221

VL - 132

SP - 20885

EP - 20891

JO - Advanced Materials

JF - Advanced Materials

SN - 0935-9648

IS - 46

ER -