Phenazineoxonium chloranilatomanganate and chloranilatoferrate: synthesis, structure, magnetic properties, and Mössbauer spectra

Шилов, Г. В.; Nikitina, Z. K.; Ovanesyan, N. S.; Алдошин, С. М.; Makhaev, V. D.

doi:10.1007/s11172-011-0190-z

Cited by 27 publications

(22 citation statements)

References 37 publications

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“…The charge transport behavior of chloranilate frameworks with the same overall honeycomb structure and mixed-valent Fe II/III was also studied. The first report, by Shilov et al, 157 discussed the structure and electronic properties of [Fe II Fe III (Cl 2 dhbq 2– ) 2 (Cl 2 dhbq 3– • )] 2– . Unlike the aforementioned [Fe III 2 (Cl 2 dhbq) 3 ] 2– system, in which the charge balancing (Me 2 NH) + ions are located mainly inside the pores, the framework charge in the mixed-valent Fe II/III framework is balanced by hydrogen-bonded layers of [(H 3 O) 2 (phenazine)] 2+ .…”

Section: Extended Conjugationmentioning

confidence: 99%

Electrically Conductive Metal–Organic Frameworks

2020

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Metal–organic frameworks (MOFs) are intrinsically porous extended solids formed by coordination bonding between organic ligands and metal ions or clusters. High electrical conductivity is rare in MOFs, yet it allows for diverse applications in electrocatalysis, charge storage, and chemiresistive sensing, among others. In this Review, we discuss the efforts undertaken so far to achieve efficient charge transport in MOFs. We focus on four common strategies that have been harnessed toward high conductivities. In the “through-bond” approach, continuous chains of coordination bonds between the metal centers and ligands’ functional groups create charge transport pathways. In the “extended conjugation” approach, the metals and entire ligands form large delocalized systems. The “through-space” approach harnesses the π–π stacking interactions between organic moieties. The “guest-promoted” approach utilizes the inherent porosity of MOFs and host–guest interactions. Studies utilizing less defined transport pathways are also evaluated. For each approach, we give a systematic overview of the structures and transport properties of relevant materials. We consider the benefits and limitations of strategies developed thus far and provide an overview of outstanding challenges in conductive MOFs.

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Section: Extended Conjugationmentioning

confidence: 99%

Electrically Conductive Metal–Organic Frameworks

2020

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“…One of the most interesting anilato-based structures obtained so far are the H 2 An 2− -and Cl 2 An 2− -based honeycomb layers [47,[106][107][108][109][110]. In these 2D compounds the structure is similar to that of the oxalate honeycomb layers, but all reported systems to date are homometallic (i.e., they contain two M II or two M III ions of the same nature type).…”

Section: Introductionmentioning

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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“…42,44,48 The heterometallic nature of the 2D lattice with two different spin ground states (except in the iron−manganese derivative) leads to the observed ferrimagnetic long-range ordering.…”

Section: ■ Introductionmentioning

confidence: 99%

A Family of Layered Chiral Porous Magnets Exhibiting Tunable Ordering Temperatures

et al. 2013

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A simple change of the substituents in the bridging ligand allows tuning of the ordering temperatures, Tc, in the new family of layered chiral magnets A[M(II)M(III)(X2An)3]·G (A = [(H3O)(phz)3](+) (phz = phenazine) or NBu4(+); X2An(2-) = C6O4X2(2-) = 2,5-dihydroxy-1,4-benzoquinone derivative dianion, with M(III) = Cr, Fe; M(II) = Mn, Fe, Co, etc.; X = Cl, Br, I, H; G = water or acetone). Depending on the nature of X, an increase in Tc from ca. 5.5 to 6.3, 8.2, and 11.0 K (for X = Cl, Br, I, and H, respectively) is observed in the MnCr derivative. Furthermore, the presence of the chiral cation [(H3O)(phz)3](+), formed by the association of a hydronium ion with three phenazine molecules, leads to a chiral structure where the Δ-[(H3O)(phz)3](+) cations are always located below the Δ-[Cr(Cl2An)3](3-) centers, leading to a very unusual localization of both kinds of metals (Cr and Mn) and to an eclipsed disposition of the layers. This eclipsed disposition generates hexagonal channels with a void volume of ca. 20% where guest molecules (acetone and water) can be reversibly absorbed. Here we present the structural and magnetic characterization of this new family of anilato-based molecular magnets.

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Phenazineoxonium chloranilatomanganate and chloranilatoferrate: synthesis, structure, magnetic properties, and Mössbauer spectra

Cited by 27 publications

References 37 publications

Electrically Conductive Metal–Organic Frameworks

Electrically Conductive Metal–Organic Frameworks

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

A Family of Layered Chiral Porous Magnets Exhibiting Tunable Ordering Temperatures

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