Electronic Conductivity, Ferrimagnetic Ordering, and Reductive Insertion Mediated by Organic Mixed-Valence in a Ferric Semiquinoid Metal–Organic Framework

Darago, Lucy E.; Aubrey, Michael L.; Yu, Chung-Jong; Gonzalez, Miguel I.; Long, Jeffrey R.

doi:10.1021/jacs.5b10385

Cited by 368 publications

(403 citation statements)

References 77 publications

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“…40,41 This has been shown already with two MOFs based on 1,2,4,5-tetrahydroxybenzene and its derivatives, where the ligands coexist in the semiquinone and quinone states, which gives rise to high electrical conductivity (10 –3 to 10 –1 S cm –1 ). 42,43 Therefore, redox-active metal ions and organic ligands are desirable when designing electrically conductive MOFs.…”

Section: Resultsmentioning

confidence: 99%

Is iron unique in promoting electrical conductivity in MOFs?

et al. 2017

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Section: Resultsmentioning

confidence: 99%

Is iron unique in promoting electrical conductivity in MOFs?

et al. 2017

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“…More interestingly, there are other 3D tricoordinated lattices with exotic Majorana states, which have not been found in iridates but are possible in 3D MOFs. Among these, the hyperoctagon lattice or (10,3)-a structure [36][37][38][39][40][41][42][43] has Majorana Fermi surfaces, which would be destabilized by an additional time-reversal interaction leaving an odd number of nodal lines [44,45].…”

Section: Fig 1 (Color Online) (A)mentioning

confidence: 99%

Designing Kitaev Spin Liquids in Metal-Organic Frameworks

2017

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Kitaev's honeycomb lattice spin model is a remarkable exactly solvable model, which has a particular type of spin liquid (Kitaev spin liquid) as the ground state. Although its possible realization in iridates and α-RuCl3 has been vigorously discussed recently, these materials have substantial non-Kitaev direct exchange interactions and do not have a spin liquid ground state. We propose metal-organic frameworks (MOFs) with Ru 3+ (or Os 3+ ) forming the honeycomb lattice as promising candidates for a more ideal realization of Kitaev-type spin models where the direct exchange interaction is strongly suppressed. The great flexibility of MOFs allows generalization to other three-dimensional lattices, for potential realization of a variety of spin liquids such as a Weyl spin liquid.PhySH: Frustrated magnetism, Spin liquid, Quantum spin liquid, Organic compoundsIntroduction. -Quantum spin liquids, purported exotic states of quantum magnets where long-range magnetic orders are destroyed by quantum fluctuations, have been a central subject in quantum magnetism [1]. As an important theoretical breakthrough, Kitaev constructed a spin-1/2 model on the honeycomb lattice [2] with Ising interactions between spin components depending on bond orientations. Its exact solution demonstrates many intriguing properties such as fractionalized anyonic excitations. This model was later generalized to other lattices, including three-dimensional ones, still retaining the exact solvability [3]. In this paper, we call this type of model including various generalizations as Kitaev model, and its ground states as Kitaev spin liquids. Jackeli and Khaliullin [4] discovered that the "Kitaev interaction", namely bond-dependent Ising couplings, can be realized in a (111) honeycomb layer of iridates, i.e. the A 2 IrO 3 (A = Na, Li) structure, by the superexchange interaction through the oxygen ions due to the strong spin-orbit coupling of Ir 4+ in the Mott insulator limit (see also Ref.[5] for the itinerant limit).However, unfortunately, it turned out that iridates and related inorganic compounds, such as α-RuCl 3 [6], exhibit a conventional magnetic order at low enough temperatures and do not have a true spin liquid ground state. This is due to the non-Kitaev interactions, such as antiferromagnetic Heisenberg interaction, mainly coming from the direct exchange interaction between the metal ions [7]. While their finite-temperature properties still reflect the proximity to the Kitaev model [8] and thus are of great interest, the current situation calls for a more ideal realization of the Kitaev model in real materials, so that they exhibit spin liquid ground states.In this Letter, we propose such a possible realization of the Kitaev model in metal-organic frameworks (MOFs), crystalline materials consisting of metal ions and bridging organic ligands. Although MOF is a central subject in modern complex chemistry, MOFs have not attracted much attention in the context of magnetism. This is

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“…The χ M T product in 39, 40, and 41 shows a slight decrease with decreasing temperature and at lower temperature they show a major decrease, suggesting the existence of weak antiferromagnetic interactions. Reprinted with permission from Reference [184]. Copyright 2014 American Chemical Society.…”

Section: Guests Intercalation Of Hydrogen-bond-supported Layersmentioning

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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Electronic Conductivity, Ferrimagnetic Ordering, and Reductive Insertion Mediated by Organic Mixed-Valence in a Ferric Semiquinoid Metal–Organic Framework

Cited by 368 publications

References 77 publications

Is iron unique in promoting electrical conductivity in MOFs?

Is iron unique in promoting electrical conductivity in MOFs?

Designing Kitaev Spin Liquids in Metal-Organic Frameworks

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

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