Structure and magnetic ordering of a 2-D MnII(TCNE)I(OH2) (TCNE = tetracyanoethylene) organic-based magnet (Tc = 171 K)

Lapidus, Saul H.; McConnell, Amber C.; Stephens, Peter W.; Miller, Joel S.

doi:10.1039/c1cc10478k

Cited by 26 publications

(38 citation statements)

References 15 publications

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“…25) does not decrease to zero at 350 K, further suggesting the presence of superparamagnetic particles with blocking temperatures even above 350 K. These results suggest that the short Fe–Fe distance in the c direction together with the strong coupling between Fe spins mediated by the fully delocalized π- electrons along the ab plane contributes to the persistence of spontaneous magnetization above room temperature. Compared with the Curie temperatures of thus far reported magnetic MOFs 14,18,42–44 , our work discovers the layered conjugated MOF exhibiting ferromagnetic coupling above room temperature (Supplementary Table 2). However, the polycrystalline nature of the samples (10–100 nm in domain size) renders the observed superparamagnetism, which could be addressed by improving the sample preparation, such as to obtain single crystals in the future.…”

Section: Resultsmentioning

confidence: 67%

A semiconducting layered metal-organic framework magnet

et al. 2019

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The realization of ferromagnetism in semiconductors is an attractive avenue for the development of spintronic applications. Here, we report a semiconducting layered metal-organic framework (MOF), namely K 3 Fe 2 [( 2,3,9,10,16,17,23,24 -octahydroxy phthalocyaninato)Fe] (K 3 Fe 2 [PcFe-O 8 ]) with spontaneous magnetization. This layered MOF features in-plane full π-d conjugation and exhibits semiconducting behavior with a room temperature carrier mobility of 15 ± 2 cm 2 V −1 s −1 as determined by time-resolved Terahertz spectroscopy. Magnetization experiments and 57 Fe Mössbauer spectroscopy demonstrate the presence of long-range magnetic correlations in K 3 Fe 2 [PcFe-O 8 ] arising from the magnetic coupling between iron centers via delocalized π electrons. The sample exhibits superparamagnetic features due to a distribution of crystal size and possesses magnetic hysteresis up to 350 K. Our work sets the stage for the development of spintronic materials exploiting magnetic MOF semiconductors.

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Section: Resultsmentioning

confidence: 67%

A semiconducting layered metal-organic framework magnet

et al. 2019

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“…42 The observation of magnetic order at 105 K places 2 in a small group of metal-organic solids that display magnetic order above 100 K. All previously reported materials use organonitrile ligands as linkers between metals, the most highlystudied of these examples being TCNE (tetracyanoethylene) 17,43 and TCNQ (tetracyanoquinodimethane). 13,44,45 Among structurally-characterized materials, 2 is only eclipsed by two TCNE-bridged Mn II solids, Mn II [TCNE] 3/2 (I 3 ) 1/2 •0.5 THF and Mn II [TCNE]I(OH) 2 , each of which is a ferrimagnet below 171 K. 14,15 Electrical Conductivity. Bulk magnetic ordering in these compounds is accompanied by electrical conductivity, a rare occurrence in metal-organic materials.…”

Section: Resultsmentioning

confidence: 99%

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

et al. 2017

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We report the magnetism and conductivity for a redox pair of iron-quinoid metal-organic frameworks (MOFs). The oxidized compound, (MeNH)[FeL]·2HO·6DMF (LH = 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 S/cm (E = 0.26(1) cm) and 1.0(3) × 10 S/cm (E = 0.19(1) cm) in its solvated and desolvated forms, respectively. Upon soaking in a DMF solution of CpCo, the compound undergoes a single-crystal-to-single-crystal one-electron reduction to give (CpCo)(MeNH)[FeL]·4.9DMF. Structural and spectroscopic analysis confirms this reduction to be ligand-based, and as such the trianionic framework is formulated as [Fe(L)]. Magnetic measurements for this reduced compound reveal the presence of dominant intralayer metal-organic radical coupling to give a magnetically ordered phase below T = 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 S/cm with E = 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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“…In particular, TCNE and TCNQ (TCNE = tetracyanoethylene, TCNQ = 7,7,8,8tetracyanoquinodimethane) have been used to construct network magnets with voids and high ordering temperatures. However, the weak coordination bonds between these ligands and the transition metal centers make it difficult to obtain robust permanent pores in the structures [123][124][125]. Such an issue had not been solved until 2015, when the Harris group utilized a semiquinoid ligand, 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone to synthesize a radical-bridging MOF, (Me 2 NH 2 ) 2 [Fe 2 L 3 ]•2H 2 O•6DMF (DMF = dimethylformamide), that had an ordering temperature of 80 K and a BET surface area of 885 m 2 /g [126].…”

Section: Magnetismmentioning

confidence: 99%

Metal–Organic Frameworks as Versatile Platforms for Organometallic Chemistry

et al. 2021

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Metal–organic frameworks (MOFs) are emerging porous materials with highly tunable structures developed in the 1990s, while organometallic chemistry is of fundamental importance for catalytic transformation in the academic and industrial world for many decades. Through the years, organometallic chemistry has been incorporated into functional MOF construction for diverse applications. Here, we will focus on how organometallic chemistry is applied in MOF design and modifications from linker-centric and metal-cluster-centric perspectives, respectively. Through structural design, MOFs can function as a tailorable platform for traditional organometallic transformations, including reaction of alkenes, cross-coupling reactions, and C–H activations. Besides, an overview will be made on other application categories of organometallic MOFs, such as gas adsorption, magnetism, quantum computing, and therapeutics.

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Structure and magnetic ordering of a 2-D MnII(TCNE)I(OH2) (TCNE = tetracyanoethylene) organic-based magnet (Tc = 171 K)

Cited by 26 publications

References 15 publications

A semiconducting layered metal-organic framework magnet

A semiconducting layered metal-organic framework magnet

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

Metal–Organic Frameworks as Versatile Platforms for Organometallic Chemistry

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Structure and magnetic ordering of a 2-D MnII(TCNE)I(OH2) (TCNE = tetracyanoethylene) organic-based magnet (Tc = 171 K)

Cited by 26 publications

References 15 publications

A semiconducting layered metal-organic framework magnet

A semiconducting layered metal-organic framework magnet

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

Metal–Organic Frameworks as Versatile Platforms for Organometallic Chemistry

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