Effect of Halopyridine Guest Molecules on the Structure and Superconducting Prop­erties of β″‐[Bis(ethylenedithio)tetra­thiafulvalene]4(H3O)[Fe(C2O4)3]·Guest Crystals

Prokhorova, Tatiana G.; Buravov, L. I.; Yagubskii, Eduard B.; Zorina, Leokadiya V.; Simonov, Sergey V.; Zverev, V. N.; Shibaeva, R. P.; Canadell, Enric

doi:10.1002/ejic.201501092

Cited by 17 publications

(19 citation statements)

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“…The conducting and structural properties of β"-crystals strongly depend on the size, shape, and chemical nature of the guest solvent molecule G. In some crystals with G = halobenzenes and M = Fe, the structural phase transition from the monoclinic to the triclinic state was found upon lowering the temperature [21,22,36]. In our recent work we showed that the same transition also exists in superconducting Fe crystals with G = 2-ClPy and 2-BrPy (T c = 4.0 K and 4.3 K, respectively) [25]. These structural transitions arise from noticeable positional shifts of all components of the complex anion, giving rise to two nonequivalent organic β" layers and the partial ordering of the ethylene groups of BEDT-TTF molecules.…”

Section: Discussionmentioning

confidence: 62%

Specific Structural Disorder in an Anion Layer and Its Influence on Conducting Properties of New Crystals of the (BEDT-TTF)4A+[M3+(ox)3]G Family, Where G Is 2-Halopyridine; M Is Cr, Ga; A+ Is [K0.8(H3O)0.2]+

et al. 2018

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New crystals (1-4) of organic conductors based on the radical cation salts of the bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) with paramagnetic and diamagnetic tris(oxalato)metallate anions {A + [M 3+ (ox) 3 ] 3− G} 2− , where M is Cr, Ga; G is 2-chloropyridine, 2-bromopyridine; and A + is [K 0.8 (H 3 O) 0.2 ] + have been prepared and their crystal structure and transport properties were studied. All crystals belong to the monoclinic group of the (BEDT-TTF) 4 A + [M 3+ (ox) 3 ]G family with β"-packing type of conducting BEDT-TTF layers. In contrast to the known superconducting crystals with M 3+ = Fe 3+ and G = 2-chloro-or 2-bromopyridine (T c = 4.0-4.3 K), crystals with Cr 3+ and Ga 3+ ions exhibit metallic properties down to 0.5 K without superconducting transition. Upon cooling these crystals, the incommensurate superstructure appears, which has never been observed before in the numerous β"-salts of the family. In addition, orthorhombic (sp. group Pbca) semiconducting crystals α"-(BEDT-TTF) 5 [Ga(ox) 3 ]·3.4·H 2 O·0.6 EtOH (5) were obtained. It is a new compound in the family of BEDT-TTF crystals with tris(oxalato)metallate anions.

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Section: Discussionmentioning

confidence: 62%

Specific Structural Disorder in an Anion Layer and Its Influence on Conducting Properties of New Crystals of the (BEDT-TTF)4A+[M3+(ox)3]G Family, Where G Is 2-Halopyridine; M Is Cr, Ga; A+ Is [K0.8(H3O)0.2]+

et al. 2018

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“…As usual, the HOMO … HOMO interactions along the step-chains are the stronger ones and those along the lateral π-type interactions are still very sizable (i.e., around 60% of those along the step-chains). In contrast with other β'' salts of BEDT-TTF and similar anionic layers, 16,17 the interactions along the stacks are clearly weaker. In terms of these HOMO … HOMO interactions the present salts are quite similar to the β''-type molecular superconductor β''-(BEDT-TTF)4Kx(H3O)1-x[Ru(C2O4)3]C6H5Br (x~0.8).…”

Section: Electronic Structurementioning

confidence: 65%

“…Guest salts where Guest is a solvent molecule. 16,17 We note that in the present salts there are several quite short C-H … O contacts linking the BEDT-TTF donors and the anion layer so that structural changes in the anion layer could subtly be transmitted to the donor layers. In addition, the two salts undergoing the metal -insulator transition are associated with smaller interlayer c parameters than those keeping the metallic character suggesting that they are more constricted and their donor layers more sensitive to structural changes in the anion layers.…”

Section: Electronic Structurementioning

confidence: 80%

2D Molecular Superconductor to Insulator Transition in the β′′-(BEDT-TTF)₂[(H₂O)(NH₄)₂M(C₂O₄)₃]·18-crown-6 Series (M = Rh, Cr, Ru, Ir)

et al. 2019

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The series of salts β"-(BEDT-TTF)2[(H2O)(NH4)2M(C2O4)3].18-crown-6 show ambient-pressure superconductivity when M = Cr or Rh. Evidence indicates that the previously reported Cr and Rh salts show a bulk Berezinski-Kosterlitz-Thouless superconducting transition. The isostructural ruthenium and iridium salts are reported here. The Ir salt represents the first radical-cation salt to contain a 5d tris(oxalato)metallate anion. Both the Ru and Ir salts do not show superconductivity but instead undergo a broad chemically-induced metal-to-insulator transition at 155 K for ruthenium and at 100 K for iridium. The c axes of the Ru and Ir salts are much shorter than those of the Rh and Cr salts. Thus the more stable metallic state of the Cr and Rh salts is associated with the more strongly 2D electronic systems. The different low-temperature behaviour of the Ru and Ir salts, which exhibit a smaller interlayer spacing, could originate from a structural change in the anionic layer which thus can be easily transmitted to the donor layers and generate a localized state. However another possibility is that it originates from Berezinski-Kosterlitz-Thouless effects.

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“…In contrast, there are many different solvents that can be found in the hexagonal cavities of the anionic layers. Thus, as it can be seen in Table 1, besides the PhCN molecule used in the first example (35) [3], there are also reported salts with PhNO 2 (3,4), pyridine (py) (1, 2), PhF (19,20), PhCl (17,18), PhBr (15, 16), PhI ( 14), 1,2-PhCl 2 (13), 2-Clpy (29, 30), 3-Clpy (33), 2-Brpy (31, 32), and mixtures of PhCN and py (5)(6)(7)(8)(9)(10)(11)(12) or PhCN with halobenzenes (21)(22)(23)(24)(25)(26)(27) and even with dimethylformamide (dmf) (28), the only non-aromatic solvent used in the β" series with Fe(III) [13].…”

Section: β"-Bedt-ttf Salts With the [Fe(c 2 O 4 ) 3 ] 3− Anionmentioning

confidence: 83%

The Peter Day Series of Magnetic (Super)Conductors

Benmansour

Gómez‐García

2021

Magnetochemistry

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Here, we review the different series of (super)conducting and magnetic radical salts prepared with organic donors of the tetrathiafulvalene (TTF) family and oxalato-based metal complexes (ox = oxalate = C2O42−). Although most of these radical salts have been prepared with the donor bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF = ET), we also include all the salts prepared with other TTF-type donors such as tetrathiafulvalene (TTF), tetramethyl-tetrathiafulvalene (TM-TTF), bis(ethylenediseleno)tetrathiafulvalene (BEST), bis(ethylenedithio)tetraselenafulvalene (BETS) and 4,5bis((2S)-2-hydroxypropylthio)-4’,5’-(ethylenedithio)tetrathiafulvalene (DMPET). Most of the oxalate-based complexes are monomers of the type [MIII(C2O4)3]3−, [Ge(C2O4)3]2− or [Cu(C2O4)2]2−, but we also include the reported salts with [Fe2(C2O4)5]4− dimers, [MII(H2O)2[MIII(C2O4)3]2]4− trimers and homo- or heterometallic extended 2D layers such as [MIIMIII(C2O4)3]− and [MII2(C2O4)3]2−. We will present the different structural families and their magnetic properties (such as diamagnetism, paramagnetism, antiferromagnetism, ferromagnetism and even long-range magnetic ordering) that coexist with interesting electrical properties (such as semiconductivity, metallic conductivity and even superconductivity). We will focus on the electrical and magnetic properties of the so-called Day series formulated as β”-(BEDT-TTF)4[A+MIII(C2O4)3]·G, which represents the largest family of paramagnetic metals and superconductors reported to date, with more than fifty reported examples.

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Effect of Halopyridine Guest Molecules on the Structure and Superconducting Properties of β″‐[Bis(ethylenedithio)tetrathiafulvalene]₄(H₃O)[Fe(C₂O₄)₃]·Guest Crystals

Cited by 17 publications

References 28 publications

Specific Structural Disorder in an Anion Layer and Its Influence on Conducting Properties of New Crystals of the (BEDT-TTF)4A+[M3+(ox)3]G Family, Where G Is 2-Halopyridine; M Is Cr, Ga; A+ Is [K0.8(H3O)0.2]+

Specific Structural Disorder in an Anion Layer and Its Influence on Conducting Properties of New Crystals of the (BEDT-TTF)4A+[M3+(ox)3]G Family, Where G Is 2-Halopyridine; M Is Cr, Ga; A+ Is [K0.8(H3O)0.2]+

2D Molecular Superconductor to Insulator Transition in the β′′-(BEDT-TTF)₂[(H₂O)(NH₄)₂M(C₂O₄)₃]·18-crown-6 Series (M = Rh, Cr, Ru, Ir)

The Peter Day Series of Magnetic (Super)Conductors

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Effect of Halopyridine Guest Molecules on the Structure and Superconducting Prop­erties of β″‐[Bis(ethylenedithio)tetra­thiafulvalene]4(H3O)[Fe(C2O4)3]·Guest Crystals

Cited by 17 publications

References 28 publications

Specific Structural Disorder in an Anion Layer and Its Influence on Conducting Properties of New Crystals of the (BEDT-TTF)4A+[M3+(ox)3]G Family, Where G Is 2-Halopyridine; M Is Cr, Ga; A+ Is [K0.8(H3O)0.2]+

Specific Structural Disorder in an Anion Layer and Its Influence on Conducting Properties of New Crystals of the (BEDT-TTF)4A+[M3+(ox)3]G Family, Where G Is 2-Halopyridine; M Is Cr, Ga; A+ Is [K0.8(H3O)0.2]+

2D Molecular Superconductor to Insulator Transition in the β′′-(BEDT-TTF)2[(H2O)(NH4)2M(C2O4)3]·18-crown-6 Series (M = Rh, Cr, Ru, Ir)

The Peter Day Series of Magnetic (Super)Conductors

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Effect of Halopyridine Guest Molecules on the Structure and Superconducting Properties of β″‐[Bis(ethylenedithio)tetrathiafulvalene]₄(H₃O)[Fe(C₂O₄)₃]·Guest Crystals

2D Molecular Superconductor to Insulator Transition in the β′′-(BEDT-TTF)₂[(H₂O)(NH₄)₂M(C₂O₄)₃]·18-crown-6 Series (M = Rh, Cr, Ru, Ir)