Molecular Charge-Transfer Salt of BEDT−TTF [Bis(ethylenedithio)tetrathiafulvalene] with the Oxalate-Bridged Dimeric Anion [Fe2(C2O4)5]4-

Rashid, Samina; Turner, Scott S.; Day, Peter; Light, Mark E.; Hursthouse, Michael B.

doi:10.1021/ic991409w

Cited by 49 publications

(20 citation statements)

References 13 publications

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“…[26] Metal oxalate dimer anions have been found in the radical cation salts (BEDT-TTF) 4 [27] and (BEDT-TTF) 5 [Cr 2 (C 2 O 4 )(NCS) 8 ]. [28] In the latter the anion has the oxalate group as a bridged tetradentate ligand, whereas the former contains the dimeric anion with one bridged tetradentate and four bidentate oxalates.…”

Section: (H 3 O)[cr(c 2 O 4 ) 3 ] 2 [(H 3 O)mentioning

confidence: 99%

Molecular Metals Based on BEDT‐TTF Radical Cation Salts with Magnetic Metal Oxalates as Counterions: β″‐(BEDT‐TTF)₄A[M(C₂O₄)₃]·DMF (A = NH₄⁺, K⁺; M = Cr^III, Fe^III)

Prokhorova

Khasanov

Zorina

et al. 2003

Adv Funct Materials

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Four (BEDT‐TTF)4A[M(C2O4)3]·DMF (DMF = dimethylformamide) salts of the organic donor molecule bis(ethylenedithio)tetrathiafulvalene (BEDT‐TTF) with metal oxalate anions, where A = (NH4, K), M = Cr (1); A = NH4, M = Fe (2); A = K, M = Cr (3); and A = NH4, M = Cr (3′) were prepared by electrocrystallization. These salts were characterized by single‐crystal X‐ray diffraction, electron spin resonance (ESR) spectroscopy, electrical resistance measurements, and electronic band structure calculations. The structures (with space group C2/c) consist of alternating β″‐type layers of BEDT‐TTF and an approximately hexagonal network formed by the A+ cation and the metal, with the solvent molecule, DMF, occupying hexagonal cavities in the anion layer. All of the salts are two‐dimensional organic metals down to 4.2 K and do not exhibit superconductivity. Their electronic band structure is similar to that of the known organic superconductor β″‐(BEDT‐TTF)4H3O[Fe(C2O4)3]·BN. The ESR spectra of salts 1 and 3′ are characterized by two resonances, one of Gaussian shape arising from the 3d localized electrons of Cr3+ and the other of Lorentzian (and Dysonian) shape due to the conduction electrons in the organic layers. On the basis of the calculated Fermi surfaces it is suggested that these salts could exhibit an interesting magnetoresistance behavior if disorder does not prevent the observation of the Shubnikov‐de Haas oscillations.

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Section: (H 3 O)[cr(c 2 O 4 ) 3 ] 2 [(H 3 O)mentioning

confidence: 99%

Molecular Metals Based on BEDT‐TTF Radical Cation Salts with Magnetic Metal Oxalates as Counterions: β″‐(BEDT‐TTF)₄A[M(C₂O₄)₃]·DMF (A = NH₄⁺, K⁺; M = Cr^III, Fe^III)

Prokhorova

Khasanov

Zorina

et al. 2003

Adv Funct Materials

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“…The [Fe 2 (C 2 O 4 ) 5 ] 4− dimers are formed by two [Fe(C 2 O 4 ) 3 ] 3− monomers with different chirality sharing an oxalate bridge (Figure 1c). There are two independent BEDT-TTF molecules, both with a +1 charge, in agreement with the 4:1 stoichiometry and the -4 charge of the anion, resulting in a semiconducting salt with a high activation energy and a low room temperature conductivity (Table 9) [58]. The oxalate-bridged Fe(III) dimer in this salt shows, as expected, a weak antiferromagnetic interaction with J = −3.44 cm −1 , similar to that found in the TTF and TM-TTF salts with the same dimer that will be described in the next section [59,60].…”

Section: Bedt-ttf Salts Withmentioning

confidence: 58%

“…The only known salt with BEDT-TTF and a dimeric anion is: (BEDT-TTF) 4 [Fe 2 (C 2 O 4 ) 5 ] (105), also reported by P. Day's group [58]. In this radical salt, the dimeric anion [Fe 2 (C 2 O 4 ) 5 ] 4− is formed in situ from the precursor [Fe(C 2 O 4 ) 3 ] 3− monomer in the electrochemical cell.…”

Section: Bedt-ttf Salts Withmentioning

confidence: 70%

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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“…The antiferromagnetic exchange interactions in 1 expected from the lowering of vT vs. T are slightly weaker than that reported for oxalato-bridged dimers, such as [Fe(acac) 4 [28] and [(biscipen)Fe(C 2 O 4 )Fe(biscipen)] (J = À5 cm À1 ) [29], for charge-transfer salts (J = À3.44 to À6.12 cm À1 ) [30,31], and for a charge-transfer complex with oxalato-bridged one-dimensional magnetic chain (J = À5.10(3) cm À1 ) [32]. The small J value is likely the result of unfavorable orientations of the magnetic orbitals [27].…”

mentioning

confidence: 69%

The system iron(II)/mpzbpy mediates the H2O2 oxidation of cyclohexane and cyclooctene and the aerobic oxidative cleavage of ascorbic acid to oxalate

Ruiter

Costa²,

Lappalainen³

et al. 2008

Inorganic Chemistry Communications

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Molecular Charge-Transfer Salt of BEDT−TTF [Bis(ethylenedithio)tetrathiafulvalene] with the Oxalate-Bridged Dimeric Anion [Fe₂(C₂O₄)₅]^4-

Cited by 49 publications

References 13 publications

Molecular Metals Based on BEDT‐TTF Radical Cation Salts with Magnetic Metal Oxalates as Counterions: β″‐(BEDT‐TTF)₄A[M(C₂O₄)₃]·DMF (A = NH₄⁺, K⁺; M = Cr^III, Fe^III)

Molecular Metals Based on BEDT‐TTF Radical Cation Salts with Magnetic Metal Oxalates as Counterions: β″‐(BEDT‐TTF)₄A[M(C₂O₄)₃]·DMF (A = NH₄⁺, K⁺; M = Cr^III, Fe^III)

The Peter Day Series of Magnetic (Super)Conductors

The system iron(II)/mpzbpy mediates the H2O2 oxidation of cyclohexane and cyclooctene and the aerobic oxidative cleavage of ascorbic acid to oxalate

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Molecular Charge-Transfer Salt of BEDT−TTF [Bis(ethylenedithio)tetrathiafulvalene] with the Oxalate-Bridged Dimeric Anion [Fe2(C2O4)5]4-

Cited by 49 publications

References 13 publications

Molecular Metals Based on BEDT‐TTF Radical Cation Salts with Magnetic Metal Oxalates as Counterions: β″‐(BEDT‐TTF)4A[M(C2O4)3]·DMF (A = NH4+, K+; M = CrIII, FeIII)

Molecular Metals Based on BEDT‐TTF Radical Cation Salts with Magnetic Metal Oxalates as Counterions: β″‐(BEDT‐TTF)4A[M(C2O4)3]·DMF (A = NH4+, K+; M = CrIII, FeIII)

The Peter Day Series of Magnetic (Super)Conductors

The system iron(II)/mpzbpy mediates the H2O2 oxidation of cyclohexane and cyclooctene and the aerobic oxidative cleavage of ascorbic acid to oxalate

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Molecular Charge-Transfer Salt of BEDT−TTF [Bis(ethylenedithio)tetrathiafulvalene] with the Oxalate-Bridged Dimeric Anion [Fe₂(C₂O₄)₅]^4-

Molecular Metals Based on BEDT‐TTF Radical Cation Salts with Magnetic Metal Oxalates as Counterions: β″‐(BEDT‐TTF)₄A[M(C₂O₄)₃]·DMF (A = NH₄⁺, K⁺; M = Cr^III, Fe^III)

Molecular Metals Based on BEDT‐TTF Radical Cation Salts with Magnetic Metal Oxalates as Counterions: β″‐(BEDT‐TTF)₄A[M(C₂O₄)₃]·DMF (A = NH₄⁺, K⁺; M = Cr^III, Fe^III)