Use of the TCNQF4 2- Dianion in the Spontaneous Redox Formation of [FeIII(L-)2][TCNQF4 -]

Ian A. Gass, Jinzhen Lu, Mousa Asadi, David W. Lupton, Craig M. Forsyth, Blaise L. Geoghegan, Boujemaa Moubaraki, John D. Cashion, Lisandra L. Martin, Alan M. Bond, Keith S. Murray

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Abstract

The reaction of [FeII(L.)2](BF4)2 with Li2TCNQF4 results in the formation of [FeIII(L-)2][TCNQF4 . -](1) where L. is the radical ligand, 4,4-dimethyl-2,2-di(2-pyridyl)oxazolidine-N-oxide and TCNQF4 is 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane. This has been characterised by X-ray diffraction, Raman and Fourier transform infrared (FTIR) spectroscopy, variable-temperature magnetic susceptibility, Mössbauer spectroscopy and electrochemistry. X-ray diffraction studies, magnetic susceptibility measurements and Raman and FTIR spectroscopy suggest the presence of low-spin FeIII ions, the anionic form (L-) of the ligand and the anionic radical form of TCNQF4; viz. TCNQF4 . -. Li2TCNQF4 reduces the [FeII(L.)2]2+ dication, which undergoes a reductively induced oxidation to form the [FeIII(L-)2]+ monocation resulting in the formation of [FeIII(L-)2][TCNQF4 . -](1), the electrochemistry of which revealed four well-separated, diffusion-controlled, one-electron, reversible processes. Mössbauer spectroscopy and electrochemical measurements suggest the presence of a minor second species, likely to be [FeII(L.)2][TCNQF4 2-].

Original languageEnglish
Pages (from-to)658-668
Number of pages11
JournalChemPlusChem
Volume83
Issue number7
DOIs
Publication statusPublished - Jul 2018

Keywords

  • Charge transfer
  • Electrochemistry
  • Iron
  • Magnetic properties
  • Radicals

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