Superconducting and Semiconducting Magnetic Charge Transfer Salts: (BEDT-TTF)4AFe(C2O4)3.cntdot.C6H5CN (A = H2O, K, NH4)

Kurmoo, Mohamedally; Graham, Anthony W.; Day, Peter; Coles, Simon J.; Hursthouse, Michael B.; Caulfield, Jason L.; Singleton, John; Pratt, F. L.; Hayes, W.; Ducasse, Laurent; Guionneau, Philippe

doi:10.1021/ja00154a022

Cited by 583 publications

(396 citation statements)

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“…The ␤Љ-͑BEDT-TTF͒ 4 ͓͑H 3 O͒M͑C 2 O 4 ͒ 3 ͔ · Y samples were grown using electrocrystallisation techniques as described elsewhere; 14,[16][17][18] they are generally ϳ3 ϫ 1 ϫ 0.5 mm 3 needles. It is possible to deduce the upper and lower faces that are parallel to the highly conducting quasi-twodimensional planes by visual inspection.…”

Section: Methodsmentioning

confidence: 99%

Robust superconducting state in the low-quasiparticle-density organic metalsβ″−(BEDT−TTF)4[(
Bangura
¹
,
Coldea
²
,
Singleton
³

et al. 2005
Phys. Rev. B

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We report magnetotransport measurements on the quasi-two-dimensional charge-transfer salts ␤Љ-͑BEDT-TTF͒ 4 ͓͑H 3 O͒M͑C 2 O 4 ͒ 3 ͔Y, with Y =C 6 H 5 NO 2 and C 6 H 5 CN using magnetic fields of up to 45 T and temperatures down to 0.5 K. A surprisingly robust superconducting state with an in-plane upper critical field B c2ʈ Ϸ 33 T, comparable to the highest critical field of any BEDT-TTF superconductor, and critical temperature T c Ϸ 7 K is observed when M = Ga and Y =C 6 H 5 NO 2 . The presence of magnetic M ions reduces the in-plane upper critical field to Ϸ18 T for M = Cr and Y =C 6 H 5 NO 2 and M = Fe and Y =C 6 H 5 CN. Prominent Shubnikov-de Haas oscillations are observed at low temperatures and high magnetic fields, showing that the superconducting salts possess Fermi surfaces with one or two small quasi-two-dimensional pockets, their total area comprising Շ6% of the room-temperature Brillouin zone; the quasiparticle effective masses were found to be enhanced when the ion M was magnetic ͑Fe or Cr͒. The low effective masses and quasiparticle densities, and the systematic variation of the properties of the ␤Љ-͑BEDT-TTF͒ 4 ͓͑H 3 O͒M͑C 2 O 4 ͒ 3 ͔Y salts with unit-cell volume points to the possibility of a superconducting groundstate with a charge-fluctuation-mediated superconductivity mechanism such as that proposed by Merino and McKenzie ͓Phys. Rev. Lett. 87, 237002 ͑2001͔͒, rather than the spin-fluctuation mechanism appropriate for the -͑BEDT-TTF͒ 2 X salts.

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Section: Methodsmentioning

confidence: 99%

Robust superconducting state in the low-quasiparticle-density organic metalsβ″−(BEDT−TTF)4[(
Bangura
¹
,
Coldea
²
,
Singleton
³

et al. 2005
Phys. Rev. B

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“…In conclusion, this family of anionic complexes are versatile precursors (i) for constructing 2D molecule-based Ferrimagnets with tunable ordering temperature as a function of the halogen electronegativity (Section 2.2); (ii) as magnetic components for building up multifunctional molecular materials based on BEDT-TTF organic donors-based conductivity carriers (Section 3.2), in analogy with the relevant class of [M(ox)3] 3− tris-chelated complexes which have produced the first family of molecular paramagnetic superconductors [122][123][124]. Moreover, the ability of chlorocyananilate to In conclusion, this family of anionic complexes are versatile precursors (i) for constructing 2D molecule-based Ferrimagnets with tunable ordering temperature as a function of the halogen electronegativity (Section 2.2); (ii) as magnetic components for building up multifunctional molecular materials based on BEDT-TTF organic donors-based conductivity carriers (Section 3.2), in analogy with the relevant class of [M(ox) 3 ] 3− tris-chelated complexes which have produced the first family of molecular paramagnetic superconductors [122][123][124]. Moreover, the ability of chlorocyananilate to work as the antenna ligand towards lanthanides, showing intense, sharp and long-lived emissions, represents a challenge due to the pletora of optical uses spanning from display devices and luminescent sensors to magnetic/luminescent multifunctional molecular materials.…”

Section: Molecular Paramagnetsmentioning

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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“…15 The latter is formed in 30% yield by reaction of dithiolate 5 with the enantiopure cyclic sulfate ester 50 which is prepared in two steps from the corresponding R,R-butane-2,3-diol via cyclic sulfite ester 49 (Scheme 6). Dunitz 4 -showing metallic behaviour in the plane of the layers of donor molecules. 29 For the perchlorate and tetrafluoroborate 3:2 salts, anions lie in large channels surrounded by methyl groups, and are positionally disordered (Fig.…”

Section: Alkyl Substituted Etsmentioning

confidence: 99%

“…The greatest interest is in the low temperature solid state physics, especially of the superconducting systems, since the salts are clean systems whose electrical structures can be modeled. Further highlights include a paramagnetic superconducting radical cation salt with [Fe(oxalate) 3 ] 3-, 4 and a layered salt with a mixed chromium(III) / manganese (II) oxalate network which has independent electrical and ferromagnetic properties. 5 The main variations to the ET structure have been to interchange some sulfur atoms for another Group VIB element, 6 or to vary the positions of the S atoms.…”

Section: Introductionmentioning

confidence: 99%

Substituted BEDT‐TTF Derivatives: Synthesis, Chirality, Properties and Potential Applications

Wallis

Griffiths

2005

ChemInform

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Abstract.The increasing availability of functionalized BEDT-TTF derivatives in both racemic and enantiopure forms opens up great opportunities for preparing multifunctional materials and chiral conducting systems in the form of crystals, thin films and polymers. Functionalities such as amino and carboxyl will allow attachment to other molecular systems, while intermolecular interactions between substituents, e.g. hydrogen bonding and halegon---halegon interactions, provides additional tools for designing solid state radical cation structures. In this review the syntheses of substituted derivatives of BEDT-TTF and closely related donors are surveyed, along with the structures and properties of the radical cation salts so far prepared, as a stimulus for future application of these versatile and attractive molecules. Particular attention is paid to the preparation of single enantiomers, and to the stereochemical consequences of the synthetic procedures. IntroductionOrganosulfur donor molecules have been a major focus for research in the preparation of molecular conducting systems, with tetrathiafulvalene 1 and its derivatives playing a leading role initially.1 However, breakthroughs in the last decade for preparing superconducting and hybrid materials have featured bis(ethylenedithio)tetrathiafulvalene 2, also known as BEDT-TTF or ET.2 This molecule shows two reversible oxidations at 0.50 and 0.91 V relative to the Ag/AgCl electrode, ca. 0.15 V more positive than those for TTF, and has been converted into a very large number of radical cation salts. These have been studied by a wide range of techniques stimulated in part by formation of superconducting radical cation salts with anions Cu(NCS) 2

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Superconducting and Semiconducting Magnetic Charge Transfer Salts: (BEDT-TTF)4AFe(C2O4)3.cntdot.C6H5CN (A = H2O, K, NH4)

Cited by 583 publications

References 6 publications

Robust superconducting state in the low-quasiparticle-density organic metalsβ″−(BEDT−TTF)4[(
Bangura
¹
,
Coldea
²
,
Singleton
³

et al. 2005
Phys. Rev. B

Robust superconducting state in the low-quasiparticle-density organic metalsβ″−(BEDT−TTF)4[(
Bangura
¹
,
Coldea
²
,
Singleton
³

et al. 2005
Phys. Rev. B

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

Substituted BEDT‐TTF Derivatives: Synthesis, Chirality, Properties and Potential Applications

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Superconducting and Semiconducting Magnetic Charge Transfer Salts: (BEDT-TTF)4AFe(C2O4)3.cntdot.C6H5CN (A = H2O, K, NH4)

Cited by 583 publications

References 6 publications

Robust superconducting state in the low-quasiparticle-density organic metalsβ″−(BEDT−TTF)4[(Bangura1, Coldea2, Singleton3 et al. 2005Phys. Rev. B

Robust superconducting state in the low-quasiparticle-density organic metalsβ″−(BEDT−TTF)4[(Bangura1, Coldea2, Singleton3 et al. 2005Phys. Rev. B

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

Substituted BEDT‐TTF Derivatives: Synthesis, Chirality, Properties and Potential Applications

Contact Info

Product

Resources

About

Robust superconducting state in the low-quasiparticle-density organic metalsβ″−(BEDT−TTF)4[(
Bangura
¹
,
Coldea
²
,
Singleton
³

et al. 2005
Phys. Rev. B

Robust superconducting state in the low-quasiparticle-density organic metalsβ″−(BEDT−TTF)4[(
Bangura
¹
,
Coldea
²
,
Singleton
³

et al. 2005
Phys. Rev. B