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

doi:10.1002/cplu.201800010

The use of the TCNQF₄^2-dianion in the spontaneous redox formation of [Fe^III(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 journal › Article › peer-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 language	English
Pages (from-to)	658-668
Journal	ChemPlusChem
Volume	83
Issue number	7
DOIs	https://doi.org/10.1002/cplu.201800010
Publication status	Published - 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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@article{21a1c4b45613487587d2ec5fd7910175,

title = "The use of the TCNQF42-dianion in the spontaneous redox formation of [FeIII(L-)2][TCNQF4•-]",

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, M{\"o}ssbauer 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. M{\"o}ssbauer spectroscopy and electrochemical measurements suggest the presence of a minor second species, likely to be [FeII(L•)2][TCNQF42-].",

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

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.",

year = "2018",

month = mar,

day = "9",

doi = "10.1002/cplu.201800010",

language = "English",

volume = "83",

pages = " 658--668",

journal = "ChemPlusChem",

issn = "2192-6506",

number = "7",

}

TY - JOUR

T1 - The use of the TCNQF42-dianion in the spontaneous redox formation of [FeIII(L-)2][TCNQF4•-]

AU - Gass, Ian A.

AU - Lu, Jinzhen

AU - Asadi, Mousa

AU - Lupton, David W.

AU - Forsyth, Craig M.

AU - Geoghegan, Blaise L.

AU - Moubaraki, Boujemaa

AU - Cashion, John D.

AU - Martin, Lisandra L.

AU - Bond, Alan M.

AU - Murray, Keith S.

N1 - 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.

PY - 2018/3/9

Y1 - 2018/3/9

N2 - 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-].

AB - 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-].

U2 - 10.1002/cplu.201800010

DO - 10.1002/cplu.201800010

M3 - Article

SN - 2192-6506

VL - 83

SP - 658

EP - 668

JO - ChemPlusChem

JF - ChemPlusChem

IS - 7

ER -