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

Research output: Contribution to journalArticlepeer-review

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
Pages (from-to) 658-668
JournalChemPlusChem
Volume83
Issue number7
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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