2D Conductive Iron-Quinoid Magnets Ordering up to Tc = 105 K via Heterogenous Redox Chemistry

Jordan A. DeGayner, Ie Rang Jeon, Lei Sun, Mircea Dincă, T. David Harris

Research output: Research - peer-reviewArticle

  • 5 Citations

Abstract

We report the magnetism and conductivity for a redox pair of iron-quinoid metal-organic frameworks (MOFs). The oxidized compound, (Me2NH2)2[Fe2L3]·2H2O·6DMF (LH2 = 2,5-dichloro-3,6-dihydroxo-1,4-benzoquinone) was previously shown to magnetically order below 80 K in its solvated form, with the ordering temperature decreasing to 26 K upon desolvation. Here, we demonstrate this compound to exhibit electrical conductivity values up to σ = 1.4(7) × 10-2 S/cm (Ea = 0.26(1) cm-1) and 1.0(3) × 10-3 S/cm (Ea = 0.19(1) cm-1) in its solvated and desolvated forms, respectively. Upon soaking in a DMF solution of Cp2Co, the compound undergoes a single-crystal-to-single-crystal one-electron reduction to give (Cp2Co)1.43(Me2NH2)1.57[Fe2L3]·4.9DMF. Structural and spectroscopic analysis confirms this reduction to be ligand-based, and as such the trianionic framework is formulated as [FeIII 2(L3-•)3]3-. Magnetic measurements for this reduced compound reveal the presence of dominant intralayer metal-organic radical coupling to give a magnetically ordered phase below Tc = 105 K, one of the highest reported ordering temperatures for a MOF. This high ordering temperature is significantly increased relative to the oxidized compound, and stems from the overall increase in coupling strength afforded by an additional organic radical. In line with the high critical temperature, the new MOF exhibits magnetic hysteresis up to 100 K, as revealed by variable-field measurements. Finally, this compound is electrically conductive, with values up to σ = 5.1(3) × 10-4 S/cm with Ea = 0.34(1) eV. Taken together, these results demonstrate the unique ability of metal-quinoid MOFs to simultaneously exhibit both high magnetic ordering temperatures and high electrical conductivity.

LanguageEnglish (US)
Pages4175-4184
Number of pages10
JournalJournal of the American Chemical Society
Volume139
Issue number11
DOIs
StatePublished - Mar 22 2017

Fingerprint

Magnets
Iron
Metals
Oxidation-Reduction
Temperature
Single crystals
Electric Conductivity
Magnetic hysteresis
Spectroscopic analysis
Magnetic variables measurement
Magnetism
Structural analysis
Magnetization
Ligands
Electrons
benzoquinone

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

2D Conductive Iron-Quinoid Magnets Ordering up to Tc = 105 K via Heterogenous Redox Chemistry. / DeGayner, Jordan A.; Jeon, Ie Rang; Sun, Lei; Dincă, Mircea; Harris, T. David.

In: Journal of the American Chemical Society, Vol. 139, No. 11, 22.03.2017, p. 4175-4184.

Research output: Research - peer-reviewArticle

DeGayner, Jordan A. ; Jeon, Ie Rang ; Sun, Lei ; Dincă, Mircea ; Harris, T. David. / 2D Conductive Iron-Quinoid Magnets Ordering up to Tc = 105 K via Heterogenous Redox Chemistry. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 11. pp. 4175-4184
@article{05850093d8f541f3a1b63466bf5d857e,
title = "2D Conductive Iron-Quinoid Magnets Ordering up to Tc = 105 K via Heterogenous Redox Chemistry",
abstract = "We report the magnetism and conductivity for a redox pair of iron-quinoid metal-organic frameworks (MOFs). The oxidized compound, (Me2NH2)2[Fe2L3]·2H2O·6DMF (LH2 = 2,5-dichloro-3,6-dihydroxo-1,4-benzoquinone) was previously shown to magnetically order below 80 K in its solvated form, with the ordering temperature decreasing to 26 K upon desolvation. Here, we demonstrate this compound to exhibit electrical conductivity values up to σ = 1.4(7) × 10-2 S/cm (Ea = 0.26(1) cm-1) and 1.0(3) × 10-3 S/cm (Ea = 0.19(1) cm-1) in its solvated and desolvated forms, respectively. Upon soaking in a DMF solution of Cp2Co, the compound undergoes a single-crystal-to-single-crystal one-electron reduction to give (Cp2Co)1.43(Me2NH2)1.57[Fe2L3]·4.9DMF. Structural and spectroscopic analysis confirms this reduction to be ligand-based, and as such the trianionic framework is formulated as [FeIII 2(L3-•)3]3-. Magnetic measurements for this reduced compound reveal the presence of dominant intralayer metal-organic radical coupling to give a magnetically ordered phase below Tc = 105 K, one of the highest reported ordering temperatures for a MOF. This high ordering temperature is significantly increased relative to the oxidized compound, and stems from the overall increase in coupling strength afforded by an additional organic radical. In line with the high critical temperature, the new MOF exhibits magnetic hysteresis up to 100 K, as revealed by variable-field measurements. Finally, this compound is electrically conductive, with values up to σ = 5.1(3) × 10-4 S/cm with Ea = 0.34(1) eV. Taken together, these results demonstrate the unique ability of metal-quinoid MOFs to simultaneously exhibit both high magnetic ordering temperatures and high electrical conductivity.",
author = "DeGayner, {Jordan A.} and Jeon, {Ie Rang} and Lei Sun and Mircea Dincă and Harris, {T. David}",
year = "2017",
month = "3",
doi = "10.1021/jacs.7b00705",
volume = "139",
pages = "4175--4184",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "11",

}

TY - JOUR

T1 - 2D Conductive Iron-Quinoid Magnets Ordering up to Tc = 105 K via Heterogenous Redox Chemistry

AU - DeGayner,Jordan A.

AU - Jeon,Ie Rang

AU - Sun,Lei

AU - Dincă,Mircea

AU - Harris,T. David

PY - 2017/3/22

Y1 - 2017/3/22

N2 - We report the magnetism and conductivity for a redox pair of iron-quinoid metal-organic frameworks (MOFs). The oxidized compound, (Me2NH2)2[Fe2L3]·2H2O·6DMF (LH2 = 2,5-dichloro-3,6-dihydroxo-1,4-benzoquinone) was previously shown to magnetically order below 80 K in its solvated form, with the ordering temperature decreasing to 26 K upon desolvation. Here, we demonstrate this compound to exhibit electrical conductivity values up to σ = 1.4(7) × 10-2 S/cm (Ea = 0.26(1) cm-1) and 1.0(3) × 10-3 S/cm (Ea = 0.19(1) cm-1) in its solvated and desolvated forms, respectively. Upon soaking in a DMF solution of Cp2Co, the compound undergoes a single-crystal-to-single-crystal one-electron reduction to give (Cp2Co)1.43(Me2NH2)1.57[Fe2L3]·4.9DMF. Structural and spectroscopic analysis confirms this reduction to be ligand-based, and as such the trianionic framework is formulated as [FeIII 2(L3-•)3]3-. Magnetic measurements for this reduced compound reveal the presence of dominant intralayer metal-organic radical coupling to give a magnetically ordered phase below Tc = 105 K, one of the highest reported ordering temperatures for a MOF. This high ordering temperature is significantly increased relative to the oxidized compound, and stems from the overall increase in coupling strength afforded by an additional organic radical. In line with the high critical temperature, the new MOF exhibits magnetic hysteresis up to 100 K, as revealed by variable-field measurements. Finally, this compound is electrically conductive, with values up to σ = 5.1(3) × 10-4 S/cm with Ea = 0.34(1) eV. Taken together, these results demonstrate the unique ability of metal-quinoid MOFs to simultaneously exhibit both high magnetic ordering temperatures and high electrical conductivity.

AB - We report the magnetism and conductivity for a redox pair of iron-quinoid metal-organic frameworks (MOFs). The oxidized compound, (Me2NH2)2[Fe2L3]·2H2O·6DMF (LH2 = 2,5-dichloro-3,6-dihydroxo-1,4-benzoquinone) was previously shown to magnetically order below 80 K in its solvated form, with the ordering temperature decreasing to 26 K upon desolvation. Here, we demonstrate this compound to exhibit electrical conductivity values up to σ = 1.4(7) × 10-2 S/cm (Ea = 0.26(1) cm-1) and 1.0(3) × 10-3 S/cm (Ea = 0.19(1) cm-1) in its solvated and desolvated forms, respectively. Upon soaking in a DMF solution of Cp2Co, the compound undergoes a single-crystal-to-single-crystal one-electron reduction to give (Cp2Co)1.43(Me2NH2)1.57[Fe2L3]·4.9DMF. Structural and spectroscopic analysis confirms this reduction to be ligand-based, and as such the trianionic framework is formulated as [FeIII 2(L3-•)3]3-. Magnetic measurements for this reduced compound reveal the presence of dominant intralayer metal-organic radical coupling to give a magnetically ordered phase below Tc = 105 K, one of the highest reported ordering temperatures for a MOF. This high ordering temperature is significantly increased relative to the oxidized compound, and stems from the overall increase in coupling strength afforded by an additional organic radical. In line with the high critical temperature, the new MOF exhibits magnetic hysteresis up to 100 K, as revealed by variable-field measurements. Finally, this compound is electrically conductive, with values up to σ = 5.1(3) × 10-4 S/cm with Ea = 0.34(1) eV. Taken together, these results demonstrate the unique ability of metal-quinoid MOFs to simultaneously exhibit both high magnetic ordering temperatures and high electrical conductivity.

UR - http://www.scopus.com/inward/record.url?scp=85015827560&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85015827560&partnerID=8YFLogxK

U2 - 10.1021/jacs.7b00705

DO - 10.1021/jacs.7b00705

M3 - Article

VL - 139

SP - 4175

EP - 4184

JO - Journal of the American Chemical Society

T2 - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 11

ER -