2D Conductive Iron-Quinoid Magnets Ordering up to T[subscript c] = 105 K via Heterogenous Redox Chemistry
Author(s)
DeGayner, Jordan A.
Jeon, Ie-Rang
Harris, T. David
Sun, Lei
Dinca, Mircea
Date Issued
March 2017
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
DeGayner, Jordan A., et al. “2D Conductive Iron-Quinoid Magnets Ordering up to T[subscript c] = 105 K via Heterogenous Redox Chemistry.” Journal of the American Chemical Society, vol. 139, no. 11, Mar. 2017, pp. 4175–84. © 2017 American Chemical Society
Version
Author's final manuscript
Abstract
We report the magnetism and conductivity for a redox pair of iron-quinoid metal–organic frameworks (MOFs). The oxidized compound, (Me[subscript 2]NH[subscript 2])2[Fe[subscript 2]L[subscript 3]]·2H[subscript 2]O·6DMF (LH[subscript 2] = 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[superscipt –2] S/cm (Ea = 0.26(1) cm[subscript –1]) and 1.0(3) × 10[subscript –3] S/cm (Ea = 0.19(1) cm[subscript –1]) in its solvated and desolvated forms, respectively. Upon soaking in a DMF solution of Cp[subscript 2]Co, the compound undergoes a single-crystal-to-single-crystal one-electron reduction to give (Cp[subscript 2]Co)[subscript 1.43](Me[subscript 2]NH2)[subscript 1.57][Fe[subscript 2]L[subscript 3]]·4.9DMF. Structural and spectroscopic analysis confirms this reduction to be ligand-based, and as such the trianionic framework is formulated as [Fe[superscript III][subscript 2](L3[superscript –•])[subscript 3]][superscript 3–]. Magnetic measurements for this reduced compound reveal the presence of dominant intralayer metal–organic radical coupling to give a magnetically ordered phase below T[subscript c] = 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[superscript –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.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/jacs.7b00705
