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12H-Quinoxalino[2,3-b]phenoxazinium complexes with CoII and ZnII hexafluoroacetylacetonates: synthesis, structure, and properties

  • V. I. Minkin,
  • S. M. Aldoshin,
  • N. I. Omelichkin,
  • G. V. Shilov,
  • D. V. Korchagin,
  • E. I. Kunitsyna,
  • N. I. Makarova,
  • A. G. Starikov,
  • G. S. Borodkin,
  • P. A. Knyazev,
  • E. P. Ivakhnenko

摘要

Reactions of 12H-quinoxaline[2,3-b]phenoxazine (QOPO) derivatives with the CoII and ZnII hexafluoroacetylacetonates accompanied by protonation of the starting bases result in stable complexes [QOPOH]+[M(hfac)3] whose structure was determined by X-ray diffraction and by 1H and 15N NMR spectroscopy. The complexes are characterized by long-wavelength absorption (560–664 nm) and fluorescence in the red region (λfl = 674–805 nm). The relative energies of the protonated tautomers N(14)—H and N(7)—H were determined using the results of B3LYP–D3BJ/6-311G++(d,p) density functional calculations with inclusion of D3BJ dispersion correction. A SQUID magnetometry study of the static and dynamic magnetic properties of the CoII complex revealed that it behaves as a field-induced single-ion magnet.