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2D Conductive Iron-Quinoid Magnets Ordering up to Tc = 105 K via Heterogenous Redox Chemistry
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-03-13 , DOI: 10.1021/jacs.7b00705 Jordan A. DeGayner 1 , Ie-Rang Jeon 1 , Lei Sun 2 , Mircea Dincă 2 , T. David Harris 1
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-03-13 , DOI: 10.1021/jacs.7b00705 Jordan A. DeGayner 1 , Ie-Rang Jeon 1 , Lei Sun 2 , Mircea Dincă 2 , T. David Harris 1
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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]·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 [FeIII2(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.
中文翻译：
通过多相氧化还原化学订购高达 Tc = 105 K 的 2D 导电铁醌磁铁
我们报告了铁-醌型金属-有机骨架 (MOF) 氧化还原对的磁性和电导率。氧化的化合物，(Me2NH2)2[Fe2L3]·2H2O·6DMF（LH2 = 2,5-dichloro-3,6-dihydroxo-1,4-benzoquinone）以前被证明在其溶剂化形式中在低于 80 K 时磁性有序，随着去溶剂化，排序温度降低到 26 K。在这里，我们证明该化合物的电导率值高达 σ = 1.4(7) × 10-2 S/cm (Ea = 0.26(1) cm-1) 和 1.0(3) × 10-3 S/cm ( Ea = 0.19(1) cm-1) 分别为溶剂化和去溶剂化形式。在 Cp2Co 的 DMF 溶液中浸泡后，该化合物经历单晶到单晶的单电子还原，得到 (Cp2Co)1.43(Me2NH2)1.57[Fe2L3]·4.9DMF。结构和光谱分析证实这种减少是基于配体的，因此，三阴离子骨架被公式化为[FeIII2(L3-•)3]3-。对这种还原化合物的磁性测量表明，存在占主导地位的层内金属-有机自由基偶联，以提供低于 Tc = 105 K 的磁性有序相，这是报道的 MOF 最高有序温度之一。这种高有序温度相对于氧化化合物显着增加，并且源于额外的有机基团提供的偶联强度的整体增加。与高临界温度一致，新的 MOF 表现出高达 100 K 的磁滞，如可变场测量所示。最后，该化合物具有导电性，其值高达 σ = 5.1(3) × 10-4 S/cm，Ea = 0.34(1) eV。综合起来，
更新日期：2017-03-13
中文翻译：
通过多相氧化还原化学订购高达 Tc = 105 K 的 2D 导电铁醌磁铁
我们报告了铁-醌型金属-有机骨架 (MOF) 氧化还原对的磁性和电导率。氧化的化合物，(Me2NH2)2[Fe2L3]·2H2O·6DMF（LH2 = 2,5-dichloro-3,6-dihydroxo-1,4-benzoquinone）以前被证明在其溶剂化形式中在低于 80 K 时磁性有序，随着去溶剂化，排序温度降低到 26 K。在这里，我们证明该化合物的电导率值高达 σ = 1.4(7) × 10-2 S/cm (Ea = 0.26(1) cm-1) 和 1.0(3) × 10-3 S/cm ( Ea = 0.19(1) cm-1) 分别为溶剂化和去溶剂化形式。在 Cp2Co 的 DMF 溶液中浸泡后，该化合物经历单晶到单晶的单电子还原，得到 (Cp2Co)1.43(Me2NH2)1.57[Fe2L3]·4.9DMF。结构和光谱分析证实这种减少是基于配体的，因此，三阴离子骨架被公式化为[FeIII2(L3-•)3]3-。对这种还原化合物的磁性测量表明，存在占主导地位的层内金属-有机自由基偶联，以提供低于 Tc = 105 K 的磁性有序相，这是报道的 MOF 最高有序温度之一。这种高有序温度相对于氧化化合物显着增加，并且源于额外的有机基团提供的偶联强度的整体增加。与高临界温度一致，新的 MOF 表现出高达 100 K 的磁滞，如可变场测量所示。最后，该化合物具有导电性，其值高达 σ = 5.1(3) × 10-4 S/cm，Ea = 0.34(1) eV。综合起来，
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