(Azulene‐1,3‐diyl)‐bis(nitronyl nitroxide) and (Azulene‐1,3‐diyl)‐bis(iminonitroxide) and Their Copper Complexes

(Azulene‐1,3‐diyl)‐bis(nitronyl nitroxide) and (Azulene‐1,3‐diyl)‐bis(iminonitroxide) and Their Copper Complexes Full article

Journal

Chemistry - An Asian Journal
ISSN: 1861-4728

Output data

Year: 2017, Volume: 12, Number: 22, Pages: 2929-2941 Pages count : 13 DOI: 10.1002/asia.201701085

Tags

azulenes · copper · nonalternanthydrocarbons · quantum chemistry · radicals

Authors

Haraguchi Makoto ¹ , Tretyakov Evgeny ^2,3 , Gritsan Nina ^2,4 , Romanenko Galina ⁵ , Gorbunov Dmitry ^2,4 , Bogomyakov Artem ⁵ , Maryunina Kseniya ⁶ , Suzuki Shuichi ^1,7 , Kozaki Masatoshi ¹ , Shiomi Daisuke ¹ , Sato Kazunobu ¹ , Takui Takeji ¹ , Nishihara Sadafumi ⁶ , Inoue Katsuya ⁶ , Okada Keiji ^1,8

Affiliations

1	Department of Chemistry and Molecular Materials Science, Graduate School of Science, Osaka City University, Sugimoto, Sumiyoshi-ku, Osaka, 558-8585 Japan
2	Novosibirsk State University, Pirogova Street, 2, 630090 Novosibirsk, Russian Federation
3	Vorozhtsov Institute of Organic Chemistry, Russian Academy of Sciences, Ak. Lavrentiev Avenue 9, 630090 Novosibirsk, Russian Federation
4	Voevodsky Institute of Chemical Kinetics and Combustion, 3 ul. Institutskaya, 630090 Novosibirsk, Russian Federation
5	International Tomography Center, Russian Academy of Sciences, 3a ul. Institutskaya, 630090 Novosibirsk, Russian Federation
6	Department of Chemistry, Graduate School of Science, Center for Chiral Science and Institute for Advanced Materials Research, Hiroshima University, 1-3-1, Kagamiyama, Higashi-Hiroshima, 739-8526 Japan
7	Graduate School of Science, Osaka University, Toyonaka, Osaka, 560-8531 Japan
8	The Osaka City University Advanced Research Institute for Natural Science and Technology (OCARINA), Sugimoto, Sumiyoshi-ku, Osaka, 558-8585 Japan

In contrast to diradicals connected by alternant hydrocarbons, only a few studies on those connected by nonalternant hydrocarbons have been reported. The syntheses, structures, and magnetic properties of azulene-1,3-diyl linked bis(nitronyl nitroxide) (NN2Az) and bis(iminonitroxide) (IN2Az) diradicals and their Cu(hfac)2 complexes were investigated. NN2Az was shown to have an intramolecular ferromagnetic interaction with Jobs/kB = +10.0 K (H = 2JS1S2) between (nitronyl nitroxide) spins, whereas IN2Az was estimated to have a much weaker intramolecular magnetic interaction. The reactions of NN2Az and IN2Az with Cu(hfac)2 gave a 1:2 [(Cu(hfac)2)2(NN2Az)] complex and a 1:1 [Cu(hfac)2(IN2Az)]•C6H12 complex, respectively. [(Cu(hfac)2)2(NN2Az)] showed strong intramolecular AF interactions (J1-Cu-R/kB  –800 K, J2-Cu-R/kB  –500 K) were observed between the Cu(II)- and the coordinating NN-spins, while [Cu(hfac)2(IN2Az)] exhibited a ferromagnetic exchange interaction (Jobs-Cu–R/kB = +114 K) between the Cu(II)- and the imino-coordinated iminonitroxide-spins.

Haraguchi M. , Tretyakov E. , Gritsan N. , Romanenko G. , Gorbunov D. , Bogomyakov A. , Maryunina K. , Suzuki S. , Kozaki M. , Shiomi D. , Sato K. , Takui T. , Nishihara S. , Inoue K. , Okada K.
(Azulene‐1,3‐diyl)‐bis(nitronyl nitroxide) and (Azulene‐1,3‐diyl)‐bis(iminonitroxide) and Their Copper Complexes
Chemistry - An Asian Journal. 2017. V.12. N22. P.2929-2941. DOI: 10.1002/asia.201701085 WOS Scopus

Web of science:	WOS:000415372600012
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