The use of the TCNQF42-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-tetracyano-quinodimethane. This has been characterised by x-ray diffraction, Raman and Fourier-transform infra-red (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 ion, the anionic form (L-­) of the ligand and the anionic radical form of TCNQF4; 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][TCNQF42-].
Original languageEnglish
JournalChemPlusChem
DOIs
Publication statusPublished - 9 Mar 2018

Bibliographical note

This is the peer reviewed version of the following article: Gass, I. A., Lu, J. , Asadi, M. , Lupton, D. W., Forsyth, C. M., Geoghegan, B. L., Moubaraki, B. , Cashion, J. D., Martin, L. L., Bond, A. M. and Murray, K. S. (2018), Use of the TCNQF42− Dianion in the Spontaneous Redox Formation of [FeIII(L−)2][TCNQF4⋅−] . ChemPlusChem., which has been published in final form at https://onlinelibrary.wiley.com/doi/abs/10.1002/cplu.201800010. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.

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