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 journalArticleResearchpeer-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
JournalChemPlusChem
DOIs
Publication statusPublished - 9 Mar 2018

Fingerprint

Electrochemistry
Magnetic susceptibility
Infrared spectroscopy
Fourier transforms
Spectroscopy
Ligands
Oxides
Diffraction
Ions
X ray diffraction
X rays
Oxidation
Electrons
Temperature
Oxidation-Reduction
oxazolidine

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.

Cite this

Gass, Ian A. ; Lu, Jinzhen ; Asadi, Mousa ; Lupton, David W. ; Forsyth, Craig M. ; Geoghegan, Blaise L. ; Moubaraki, Boujemaa ; Cashion, John D. ; Martin, Lisandra L. ; Bond, Alan M. ; Murray, Keith S. / The use of the TCNQF42-dianion in the spontaneous redox formation of [FeIII(L-)2][TCNQF4•-]. In: ChemPlusChem. 2018.
@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 = "3",
day = "9",
doi = "10.1002/cplu.201800010",
language = "English",
journal = "ChemPlusChem",
issn = "2192-6506",

}

Gass, IA, Lu, J, Asadi, M, Lupton, DW, Forsyth, CM, Geoghegan, BL, Moubaraki, B, Cashion, JD, Martin, LL, Bond, AM & Murray, KS 2018, 'The use of the TCNQF42-dianion in the spontaneous redox formation of [FeIII(L-)2][TCNQF4•-]', ChemPlusChem. https://doi.org/10.1002/cplu.201800010

The use of the TCNQF42-dianion in the spontaneous redox formation of [FeIII(L-)2][TCNQF4•-]. / Gass, Ian A.; Lu, Jinzhen; Asadi, Mousa; Lupton, David W.; Forsyth, Craig M.; Geoghegan, Blaise L.; Moubaraki, Boujemaa; Cashion, John D.; Martin, Lisandra L.; Bond, Alan M.; Murray, Keith S.

In: ChemPlusChem, 09.03.2018.

Research output: Contribution to journalArticleResearchpeer-review

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

JO - ChemPlusChem

JF - ChemPlusChem

SN - 2192-6506

ER -