Radical-cation salt with novel BEDT-TTF packing motif containing tris(oxalato)germanate(IV)

Lopez, Jordan R.; Akutsu, Hiroki; Martin, Lee

doi:10.1016/j.synthmet.2015.07.019

Cited by 7 publications

(6 citation statements)

References 25 publications

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“…Within each group of the four BEDT-TTF molecules, the two central ones (B and C) are completely ionized, whereas the external ones (A and D) are neutral, resulting in (BEDT-TTF) 2 2+ dimers surrounded by neutral monomers from the electronic point of view. This charge distribution results in a semiconducting behavior, as observed experimentally (Table 8) [55]. The anionic layer is also original.…”

Section: Other Phases Of Bedt-ttf Salts With [M(c O 4 ) 3 ] 3− Anionssupporting

confidence: 69%

“…Disordered CH 2 Cl 2 molecules are located between the [Ge(C 2 O 4 ) 3 ] 2− dimers. [55]. This salt also presents alternating cationic and anionic layers (Figure 26b), both layers being original.…”

Section: Other Phases Of Bedt-ttf Salts With [M(c O 4 ) 3 ] 3− Anionsmentioning

confidence: 97%

“…H atoms are omitted for clarity.Although salts 97-99 were prepared with the NH 4 + salt of the [Ge(C 2 O 4 ) 3 ] 2− dianion, the NH 4 + cation did not enter in the structure of the salts. Attempts to change the cation, using the Cs + salt, led to a new and original salt, although without the Cs + cation: (BEDT-TTF) 4 [Ge(C 2 O 4 ) 3 ].0.5CH 2 Cl 2 (100)[55]. This salt also presents alternating cationic and anionic layers (Figure26b), both layers being original.…”

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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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Section: Other Phases Of Bedt-ttf Salts With [M(c O 4 ) 3 ] 3− Anionssupporting

confidence: 69%

Section: Other Phases Of Bedt-ttf Salts With [M(c O 4 ) 3 ] 3− Anionsmentioning

confidence: 97%

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The Peter Day Series of Magnetic (Super)Conductors

Benmansour

Gómez‐García

2021

Magnetochemistry

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“…Changing the charge on the metal from 3+ to 4+ using germanium produces very different phases: (BEDT-TTF)2[Ge(C2O4)3]•benzonitrile, 17 (BEDT-TTF)5[Ge(C2O4)3]2, 18 (BEDT-TTF)7[Ge(C2O4)3]2(CH2Cl2)0.87(H2O)0.09 18 and BEDT-TTF4[Ge(C2O4)3].0.5CH2Cl2. 19 Three cases have been observed where the crown ether used to aid dissolution of the anion is included in the radical-cation salt e.g.…”

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Molecular conductors from bis(ethylenedithio)tetrathiafulvalene with tris(oxalato)rhodate

et al. 2017

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This article reports a family of new radical-cation salts of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) with tris(oxalato)rhodate: three salts with the formula β''-(BEDT-TTF)[(cation)Rh(CO)]·solvent (solvent = fluorobenzene, chlorobenzene, or bromobenzene) and one with the formula pseudo-κ-(BEDT-TTF)[(NH)Rh(CO)]·benzonitrile. We report here the syntheses, crystal structures, electrical properties and Raman spectroscopy of these new molecular conductors. The bromobenzene salt shows a decrease in resistivity below 2.5 K indicative of a superconducting transition and a Shubnikov-de Haas oscillation with a frequency of 232 T and effective mass m* of 1.27m.

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“…) 2 [Ge(C 2 O 4 ) 3 ]•PhCN,[53] (BEDT-TTF)5 [Ge(C 2 O 4 ) 3 ] 2 ,[54] (BEDT-TTF)7 [Ge(C 2 O 4 ) 3 ] 2 (CH 2 Cl 2 ) 0.87 (H 2 O) 0.09 ,[54] and (BEDT-TTF) 4 Ge(C 2 O 4 ) 3 •(CH 2 Cl 2 ) 0.50 [55]. None of these salts have anion layers with the 2D honeycomb tris(oxalato)metallate sheets found in the 3-salts.…”

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Molecular conductors of BEDT-TTF with tris(oxalato)metallate anions

Martin

2018

Coordination Chemistry Reviews

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This review presents the synthesis, crystal structures and conducting properties of BEDT-TTF radicalcation salts with the tris(oxalato)metallate anion [BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene]. This series has received much attention owing to the wide variety of conducting properties that have been observed. As well as including numerous metals, semiconductors and insulators, there are over twenty superconductors in this series. The series also includes several examples of multifunctionality where it has been possible to combine together particular physical properties in the same lattice such as electrical conductivity with magnetism, chirality or proton conductivity. This review presents an overview of the flexibility of the coordination chemistry of the oxalate ligand and the variety of packing arrangements of the tris(oxalato)metallate complexes in the insulating layers of these radical-cation salts. 4:1 radical cation-salts of BEDT-TTF with tris(oxalato)metallate(III)Research into magnetic molecule-based materials that also exhibit conductivity by the group of Prof. Peter Day at the Royal Institution of Great Britain led to the discovery in 1995 of the first molecular paramagnetic superconductor in the radical-cation salt β"-(BEDT-TTF) 4 [(H 3 O)Fe(C 2 O 4 ) 3 ]•PhCN (Fig.

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Radical-cation salt with novel BEDT-TTF packing motif containing tris(oxalato)germanate(IV)

Abstract: Abstract:The synthesis, crystal structure and resistivity of a new semiconducting BEDT-TTF radical-cation salt containing the tris(oxalato)germanate (IV)

Cited by 7 publications

References 25 publications

The Peter Day Series of Magnetic (Super)Conductors

The Peter Day Series of Magnetic (Super)Conductors

Molecular conductors from bis(ethylenedithio)tetrathiafulvalene with tris(oxalato)rhodate

Molecular conductors of BEDT-TTF with tris(oxalato)metallate anions

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