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

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) (NN2 Az) and bis(iminonitroxide) (IN2 Az) diradicals and their Cu(hfac)2 (hfac=hexafluoroacetylacetonate) complexes were investigated. NN2 Az was shown to have an intramolecular ferromagnetic interaction with Jobs /kB =+10.0 K (H=-2JS1 ⋅S2 ) between (nitronyl nitroxide) spins, whereas IN2 Az was estimated to have a much weaker intramolecular magnetic interaction. The reactions of NN2 Az and IN2 Az with Cu(hfac)2 gave a 1:2 [{Cu(hfac)2 }2 (NN2 Az)] complex and a 1:1 [Cu(hfac)2 (IN2 Az)]⋅C6 H12 complex, respectively. [{Cu(hfac)2 }2 (NN2 Az)] showed strong intramolecular antiferromagnetic interactions (J1-Cu-R /kB ≈-800 K, J2-Cu-R /kB ≈-500 K) between the CuII spins and the coordinating NN spins, whereas [Cu(hfac)2 (IN2 Az)] exhibited a ferromagnetic exchange interaction (Jobs-Cu-R /kB =+114 K) between the CuII spin and the imino-coordinated iminonitroxide spin. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Citation

Makoto Haraguchi, Evgeny Tretyakov, Nina Gritsan, Galina Romanenko, Dmitry Gorbunov, Artem Bogomyakov, Kseniya Maryunina, Shuichi Suzuki, Masatoshi Kozaki, Daisuke Shiomi, Kazunobu Sato, Takeji Takui, Sadafumi Nishihara, Katsuya Inoue, Keiji Okada. Azulene-1,3-diyl)-bis(nitronyl nitroxide) and (Azulene-1,3-diyl)-bis(iminonitroxide) and Their Copper Complexes. Chemistry, an Asian journal. 2017 Nov 16;12(22):2929-2941

PMID: 28940948

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