Design of Novel Inorganic−Organic Hybrid Materials Based on Iron-Chloranilate Mononuclear Complexes:  Characteristics of Hydrogen-Bond-Supported Layers toward the Intercalation of Guests

Nagayoshi, Kunimitsu; Kabir, Md. Khayrul; Tobita, Hiromi; Honda, Kenji; Kawahara, M.; Katada, Motomi; Adachi, Keita; Nishikawa, Hiroyuki; Ikemoto, Isao; Kumagai, Hiroo; Hosokoshi, Yuko; Inoue, Katsuya; Kitagawa, Susumu; Kawata, Satoshi

doi:10.1021/ja027895v

Cited by 50 publications

(23 citation statements)

References 80 publications

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“…First, upon reduction of 1 to 2 , the mean Fe–O bond distance increases slightly from 2.020(4) to 2.028(5) Å, although these values fall within error of one another. In both compounds, this distance can be unambiguously assigned to high-spin Fe III . , Within the bridging ligand, the mean C–C bond distance in 1 is 1.6% shorter than that in 3 , while the C–O distance is 2.9% longer in 1 . This observation is consistent with the presence of exclusively L 2– in 3 , which is therefore formulated to contain [Zn II 2 (L 2– ) 3 ] 2– , and an average of one L 2– and two L 3–• in 1 , formulated as [Fe III 2 (L 2– )(L 3–• ) 2 ] 2– .…”

Section: Resultssupporting

confidence: 63%

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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Section: Resultssupporting

confidence: 63%

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

et al. 2017

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“…The solution-based exfoliation procedure is less effective in the neutral coordination polymers which can be completely delaminated (with a thickness ca. 1-1.5 nm) [115,170,[176][177][178][179][180][181][182][183]. The stronger interlayer interactions in these hybrid compounds compared with the weaker van der Waals interactions observed in neutral 2D coordination polymers could be responsible of the lower degree of exfoliation.…”

Section: Spin-crossover Complexesmentioning

confidence: 99%

Recent Advances on Anilato-Based Molecular Materials with Magnetic and/or Conducting Properties

et al. 2017

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Abstract:The aim of the present work is to highlight the unique role of anilato-ligands, derivatives of the 2,5-dioxy-1,4-benzoquinone framework containing various substituents at the 3 and 6 positions (X = H, Cl, Br, I, CN, etc.), in engineering a great variety of new materials showing peculiar magnetic and/or conducting properties. Homoleptic anilato-based molecular building blocks and related materials will be discussed. Selected examples of such materials, spanning from graphene-related layered magnetic materials to intercalated supramolecular arrays, ferromagnetic 3D monometallic lanthanoid assemblies, multifunctional materials with coexistence of magnetic/conducting properties and/or chirality and multifunctional metal-organic frameworks (MOFs) will be discussed herein. The influence of (i) the electronic nature of the X substituents and (ii) intermolecular interactions i.e., H-Bonding, Halogen-Bonding, π-π stacking and dipolar interactions, on the physical properties of the resulting material will be also highlighted. A combined structural/physical properties analysis will be reported to provide an effective tool for designing novel anilate-based supramolecular architectures showing improved and/or novel physical properties. The role of the molecular approach in this context is pointed out as well, since it enables the chemical design of the molecular building blocks being suitable for self-assembly to form supramolecular structures with the desired interactions and physical properties.Keywords: benzoquinone derivatives; molecular magnetism; multifunctional molecular materials; spin-crossover materials; metal-organic frameworks General IntroductionThe aim of the present work is to highlight the key role of anilates in engineering new materials with new or improved magnetic and/or conducting properties and new technological applications. Only homoleptic anilato-based molecular building blocks and related materials will be discussed. Selected examples of para-/ferri-/ferro-magnetic, spin-crossover and conducting/magnetic multifunctional materials and MOFs based on transition metal complexes of anilato-derivatives, on varying the substituents at the 3,6 positions of the anilato moiety, will be discussed herein, whose structural features or physical properties are peculiar and/or unusual with respect to analogous compounds reported in the literature up to now. Their most appealing technological applications will be also reported.

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“…It is known that the chloranilate (CA) ligand and its homologues, which contain two chelating coordination sites, are capable of bridging metal centers to form monomeric molecules, chains, sheets, or 3D structures 37,39−47. Studies based on CA‐containing magneto‐networks have also been carried out with respect to the propagation of magnetic superexchange interactions between the paramagnetic metal centers through the CA bridges 37,39−47. The benefits derived from the phenazine ligand are twofold.…”

Section: Introductionmentioning

confidence: 99%

A Novel Hybrid Supramolecular Network Assembled from Perfect π−π Stacking of an Anionic Inorganic Layer and a Cationic Hydronium‐Ion‐Mediated Organic Layer

et al. 2004

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The synthesis and characterization of a three-dimensional inorganic-organic hybrid network [{Cu 2 (CA) 3 }{(H 3 O) 2 -(phz) 3 }·G] n (1; H 2 CA = chloranilic acid, phz = phenazine; G = 2CH 3 COCH 3 ·2H 2 O) is described. The crystal structure of 1 shows that the 3D network assembly is based on a combination of two types of grid-building sub-units of (6,3) topology: an anionic metal-organic coordination honeycomb grid, and a cationic hydronium-ion-mediated organic honeycomb grid.

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Design of Novel Inorganic−Organic Hybrid Materials Based on Iron-Chloranilate Mononuclear Complexes: Characteristics of Hydrogen-Bond-Supported Layers toward the Intercalation of Guests

Cited by 50 publications

References 80 publications

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

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

Recent Advances on Anilato-Based Molecular Materials with Magnetic and/or Conducting Properties

A Novel Hybrid Supramolecular Network Assembled from Perfect π−π Stacking of an Anionic Inorganic Layer and a Cationic Hydronium‐Ion‐Mediated Organic Layer

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Design of Novel Inorganic−Organic Hybrid Materials Based on Iron-Chloranilate Mononuclear Complexes: Characteristics of Hydrogen-Bond-Supported Layers toward the Intercalation of Guests

Cited by 50 publications

References 80 publications

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

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

Recent Advances on Anilato-Based Molecular Materials with Magnetic and/or Conducting Properties

A Novel Hybrid Supramolecular Network Assembled from Perfect π−π Stacking of an Anionic Inorganic Layer and a Cationic Hydronium‐Ion‐Mediated Organic Layer

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Product

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

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