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

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

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11 Citations (Scopus)

Abstract

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 (hfac=hexafluoroacetylacetonate) 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 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(IN2Az)] exhibited a ferromagnetic exchange interaction (Jobs-Cu-R/kB=+114 K) between the CuII spin and the imino-coordinated iminonitroxide spin.

Original languageEnglish
Pages (from-to)2929-2941
Number of pages13
JournalChemistry - An Asian Journal
Volume12
Issue number22
DOIs
Publication statusPublished - 16 Nov 2017

Keywords

  • azulenes
  • copper
  • nonalternant hydrocarbons
  • quantum chemistry
  • radicals
  • EXCHANGE INTERACTIONS
  • AB-INITIO
  • CORRELATION-ENERGY
  • PYRAZOLYL-SUBSTITUTED NITRONYL
  • PERTURBATION-THEORY
  • DIRADICALS
  • MAGNETIC-PROPERTIES
  • IMINO NITROXIDES
  • METAL-COMPLEXES
  • ELECTRON-DENSITY

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