Mixed Valency in a 3D Semiconducting Iron-Fluoranilate Coordination Polymer

Ryuichi Murase, Brendan Francis Abrahams, Deanna M D'Alessandro, Casey G. Davies, Timothy A Hudson, Guy N L Jameson, Boujemaa Moubaraki, Keith S. Murray, Richard Robson, Ashley L. Sutton

Research output: Contribution to journalArticleResearchpeer-review

Abstract

A pair of coordination polymers of composition (NBu4)2[M2(fan)3] (fan = fluoranilate; M = Fe and Zn) were synthesized and structurally characterized. In each case the compound consists of a pair of interpenetrating three-dimensional, (10,3)-a networks in which metal centers are linked by chelating/bridging fluoranilate ligands. Tetrabutylammonium cations are located in the spaces between the two networks. Despite the structural similarity, significant differences exist between (NBu4)2[Fe2(fan)3] and (NBu4)2[Zn2(fan)3] with respect to the oxidation states of the metal centers and ligands. For (NBu4)2[Fe2(fan)3] the structure determination as well as Mössbauer spectroscopy indicate the oxidation state for the Fe is close to +3, which contrasts with the +2 state for the Zn analogue. The differences between the two compounds extends to the ligands, with the Zn network involving only fluoranilate dianions, whereas the average oxidation state for the fluoranilate in the Fe network lies somewhere between -2 and -3. Magnetic studies on the Fe compound indicate short-range ordering. Electrochemical and spectro-electrochemical investigations indicate that the fluoranilate ligand is redox-active in both complexes; a reduced form of (NBu4)2[Fe2(fan)3] was generated by chemical reduction. Conductivity measurements indicate that (NBu4)2[Fe2(fan)3] is a semiconductor, which is attributed to the mixed valency of the fluoranilate ligands.

Original languageEnglish
Pages (from-to)9025-9035
Number of pages11
JournalInorganic Chemistry
Volume56
Issue number15
DOIs
Publication statusPublished - 7 Aug 2017

Cite this

Murase, R., Abrahams, B. F., D'Alessandro, D. M., Davies, C. G., Hudson, T. A., Jameson, G. N. L., ... Sutton, A. L. (2017). Mixed Valency in a 3D Semiconducting Iron-Fluoranilate Coordination Polymer. Inorganic Chemistry, 56(15), 9025-9035. https://doi.org/10.1021/acs.inorgchem.7b01038
Murase, Ryuichi ; Abrahams, Brendan Francis ; D'Alessandro, Deanna M ; Davies, Casey G. ; Hudson, Timothy A ; Jameson, Guy N L ; Moubaraki, Boujemaa ; Murray, Keith S. ; Robson, Richard ; Sutton, Ashley L. / Mixed Valency in a 3D Semiconducting Iron-Fluoranilate Coordination Polymer. In: Inorganic Chemistry. 2017 ; Vol. 56, No. 15. pp. 9025-9035.
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title = "Mixed Valency in a 3D Semiconducting Iron-Fluoranilate Coordination Polymer",
abstract = "A pair of coordination polymers of composition (NBu4)2[M2(fan)3] (fan = fluoranilate; M = Fe and Zn) were synthesized and structurally characterized. In each case the compound consists of a pair of interpenetrating three-dimensional, (10,3)-a networks in which metal centers are linked by chelating/bridging fluoranilate ligands. Tetrabutylammonium cations are located in the spaces between the two networks. Despite the structural similarity, significant differences exist between (NBu4)2[Fe2(fan)3] and (NBu4)2[Zn2(fan)3] with respect to the oxidation states of the metal centers and ligands. For (NBu4)2[Fe2(fan)3] the structure determination as well as M{\"o}ssbauer spectroscopy indicate the oxidation state for the Fe is close to +3, which contrasts with the +2 state for the Zn analogue. The differences between the two compounds extends to the ligands, with the Zn network involving only fluoranilate dianions, whereas the average oxidation state for the fluoranilate in the Fe network lies somewhere between -2 and -3. Magnetic studies on the Fe compound indicate short-range ordering. Electrochemical and spectro-electrochemical investigations indicate that the fluoranilate ligand is redox-active in both complexes; a reduced form of (NBu4)2[Fe2(fan)3] was generated by chemical reduction. Conductivity measurements indicate that (NBu4)2[Fe2(fan)3] is a semiconductor, which is attributed to the mixed valency of the fluoranilate ligands.",
author = "Ryuichi Murase and Abrahams, {Brendan Francis} and D'Alessandro, {Deanna M} and Davies, {Casey G.} and Hudson, {Timothy A} and Jameson, {Guy N L} and Boujemaa Moubaraki and Murray, {Keith S.} and Richard Robson and Sutton, {Ashley L.}",
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Murase, R, Abrahams, BF, D'Alessandro, DM, Davies, CG, Hudson, TA, Jameson, GNL, Moubaraki, B, Murray, KS, Robson, R & Sutton, AL 2017, 'Mixed Valency in a 3D Semiconducting Iron-Fluoranilate Coordination Polymer' Inorganic Chemistry, vol. 56, no. 15, pp. 9025-9035. https://doi.org/10.1021/acs.inorgchem.7b01038

Mixed Valency in a 3D Semiconducting Iron-Fluoranilate Coordination Polymer. / Murase, Ryuichi; Abrahams, Brendan Francis; D'Alessandro, Deanna M; Davies, Casey G.; Hudson, Timothy A; Jameson, Guy N L; Moubaraki, Boujemaa; Murray, Keith S.; Robson, Richard; Sutton, Ashley L.

In: Inorganic Chemistry, Vol. 56, No. 15, 07.08.2017, p. 9025-9035.

Research output: Contribution to journalArticleResearchpeer-review

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T1 - Mixed Valency in a 3D Semiconducting Iron-Fluoranilate Coordination Polymer

AU - Murase, Ryuichi

AU - Abrahams, Brendan Francis

AU - D'Alessandro, Deanna M

AU - Davies, Casey G.

AU - Hudson, Timothy A

AU - Jameson, Guy N L

AU - Moubaraki, Boujemaa

AU - Murray, Keith S.

AU - Robson, Richard

AU - Sutton, Ashley L.

PY - 2017/8/7

Y1 - 2017/8/7

N2 - A pair of coordination polymers of composition (NBu4)2[M2(fan)3] (fan = fluoranilate; M = Fe and Zn) were synthesized and structurally characterized. In each case the compound consists of a pair of interpenetrating three-dimensional, (10,3)-a networks in which metal centers are linked by chelating/bridging fluoranilate ligands. Tetrabutylammonium cations are located in the spaces between the two networks. Despite the structural similarity, significant differences exist between (NBu4)2[Fe2(fan)3] and (NBu4)2[Zn2(fan)3] with respect to the oxidation states of the metal centers and ligands. For (NBu4)2[Fe2(fan)3] the structure determination as well as Mössbauer spectroscopy indicate the oxidation state for the Fe is close to +3, which contrasts with the +2 state for the Zn analogue. The differences between the two compounds extends to the ligands, with the Zn network involving only fluoranilate dianions, whereas the average oxidation state for the fluoranilate in the Fe network lies somewhere between -2 and -3. Magnetic studies on the Fe compound indicate short-range ordering. Electrochemical and spectro-electrochemical investigations indicate that the fluoranilate ligand is redox-active in both complexes; a reduced form of (NBu4)2[Fe2(fan)3] was generated by chemical reduction. Conductivity measurements indicate that (NBu4)2[Fe2(fan)3] is a semiconductor, which is attributed to the mixed valency of the fluoranilate ligands.

AB - A pair of coordination polymers of composition (NBu4)2[M2(fan)3] (fan = fluoranilate; M = Fe and Zn) were synthesized and structurally characterized. In each case the compound consists of a pair of interpenetrating three-dimensional, (10,3)-a networks in which metal centers are linked by chelating/bridging fluoranilate ligands. Tetrabutylammonium cations are located in the spaces between the two networks. Despite the structural similarity, significant differences exist between (NBu4)2[Fe2(fan)3] and (NBu4)2[Zn2(fan)3] with respect to the oxidation states of the metal centers and ligands. For (NBu4)2[Fe2(fan)3] the structure determination as well as Mössbauer spectroscopy indicate the oxidation state for the Fe is close to +3, which contrasts with the +2 state for the Zn analogue. The differences between the two compounds extends to the ligands, with the Zn network involving only fluoranilate dianions, whereas the average oxidation state for the fluoranilate in the Fe network lies somewhere between -2 and -3. Magnetic studies on the Fe compound indicate short-range ordering. Electrochemical and spectro-electrochemical investigations indicate that the fluoranilate ligand is redox-active in both complexes; a reduced form of (NBu4)2[Fe2(fan)3] was generated by chemical reduction. Conductivity measurements indicate that (NBu4)2[Fe2(fan)3] is a semiconductor, which is attributed to the mixed valency of the fluoranilate ligands.

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U2 - 10.1021/acs.inorgchem.7b01038

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Murase R, Abrahams BF, D'Alessandro DM, Davies CG, Hudson TA, Jameson GNL et al. Mixed Valency in a 3D Semiconducting Iron-Fluoranilate Coordination Polymer. Inorganic Chemistry. 2017 Aug 7;56(15):9025-9035. https://doi.org/10.1021/acs.inorgchem.7b01038