Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 139, Issue 11, Pages 4175-4184Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b00705
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Funding
- National Science Foundation [DMR-1351959]
- Northwestern University
- US Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-SC0001088]
- Sloan Foundation
- Research Corporation for Science Advancement
- Dreyfus Foundation
- International Institute of Nanotechnology
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-AC02-06CH11357]
- Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource [NSF NNCI-1542205, NSF ECCS-1542205]
- State of Illinois
- International Institute for Nanotechnology (IIN)
- Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource
- MRSEC program [NSF DMR-1121262]
- Keck Foundation
- State of Illinois, through the IIN
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We report the magnetism and conductivity for a redox pair of iron-quinoid metal-organic frameworks (MOFs). The oxidized compound, (Me2NH2)(2)[Fe2L3]center dot 2H(2)O.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 sigma = 1.4(7) x 10(-2) S/cm (E-a = 0.26(1) cm(-1)) and 1.0(3) x 10(-3) S/cm (E-a = 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]center dot 4.9DMF. Structural and spectroscopic analysis confirms this reduction to be ligand-based, and as such the trianionic framework is formulated as [Fe-2(III)(L3-center dot)(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 T-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 alpha = 5.1(3) x 10(-4) S/cm with E-a = 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.
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