Improved Synthesis of the π-Electron Donor Bis(ethylenethio)tetrathiafulvalene (BET-TTF)

Pérez‐Benítez, Aarón; Tarrés, Judit; Ribera, E.; Veciana, Jaume; Rovira, Concepció

doi:10.1055/s-1999-3451

Cited by 18 publications

(20 citation statements)

References 12 publications

(17 reference statements)

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“…The synthesis of 5,6-dihydrothieno[2,3-d]-1,3-dithiol-2-one [8] and thieno[3,4-d]-1,3-dithiol-2-thione [6] was performed as previously described. The (n-Bu 4 N)[M(mnt) 2 ] (M = Au, Cu) and (n-Bu 4 N)[Au(imnt) 2 ] salts were also prepared and purified by recrystallization as previously described [20,33,34].…”

Section: Methodsmentioning

confidence: 99%

“…The coupling of 4,5-ethylenethio-1,3-dithiol-2-one (1) [8] and thiophene-1,3-dithiol-2-thione (2) [6,9] in a 1:1 proportion gave rise to a mixture of the desired donor, ETT-TTF (3), and the symmetrical byproducts bis(ethylenethio)tetrathiafulvalene (BET-TTF) and DT-TTF, which were separated by column chromatography. Owing to the formation of these symmetric derivatives, the yield of ETT-TTF (3) was low (24 %).…”

Section: Introductionmentioning

confidence: 99%

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Organic Spin Ladders from Tetrathiafulvalene (TTF) Derivatives

et al. 2005

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Starting from the first organic spin ladder reported, a dithiophene‐tetrathiafulvalene salt ((DT‐TTF)2[Au(mnt)2]) (mnt = maleonitriledithiolate), two different approaches to enlarge the family of organic spin‐ladder systems are described. The first approach consists of a molecular variation of the donor; to that purpose, the new TTF derivative ethylenethiothiophene‐tetrathiafulvalene (ETT‐TTF, 3), is synthesized and structurally characterized. From this donor a new ladder‐like structure compound, (ETT‐TTF)2[Au(mnt)2] (4), isostructural with (DT‐TTF)2[Au(mnt)2], is obtained. However, the magnetic properties of 4 do not follow the known spin‐ladder behavior owing to orientational disorder exhibited by the ETT‐TTF molecules in the crystal structure. In the second approach, the acceptor complex is changed, either in the nature of the ligand or in the metal. With the [Au(i‐mnt)2]– salt (i‐mnt = iso‐maleonitriledithiolate), the new ladder‐like compound (DT‐TTF)2[Au(i‐mnt)2] (5), isostructural with 4, is obtained, but only as a minority product. Two other compounds with a different anion generated in situ, bearing a Au(I) dimeric core, were also isolated; (DT‐TTF)9[Au2(i‐mnt)2]2 (6) as the most abundant phase and (DT‐TTF)2[Au2(i‐mnt)2] (7) as another minority phase. Salt 7 is characterized by X‐ray crystallography as a chiral compound, due to the torsion of the ligands around the central Au–Au bond. The magnetic properties of (DT‐TTF)2[Au(i‐mnt)2] (5) indicate that it follows a spin‐ladder behavior and the electron paramagnetic resonance (EPR) data is fitted to the Troyer and Barnes and Riera equations with the parameters Δ/kB = 71 K, J∥/kB = 86 K, and J⟂/kB = 142 K, indicating a J⟂/J∥ ratio of 1.65. The change of the gold complex [Au(mnt)2] for its copper analogue, [Cu(mnt)2] also leads to a ladder‐like structure, (DT‐TTF)2[Cu(mnt)2] (8), which is isostructural with the gold analogue and with salts 4 and 5. The fully ionic salt (DT‐TTF)[Cu(mnt)2] (9) is also obtained. The magnetic properties demonstrated that compound 8 is the third organic spin‐ladder system of this family, and the values found by a fitting to the ladder equations were Δ/kB = 123 K, J∥/kB = 121 K, and J⟂/kB = 218 K, corresponding to a J⟂/J∥ ratio of 1.75, similar to that of 5 and close to that of an ideal spin ladder.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Organic Spin Ladders from Tetrathiafulvalene (TTF) Derivatives

et al. 2005

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“…To the best of our knowledge, the transition metal bis(dithiothiophene) compounds, analogous to donors in which the central C=C bond is replaced by a transition metal, have not been previously obtained. Herein we report the use of ketones 1 and 2 and thione 3 , precursors for the synthesis of thiophene substituted TTF donors,16, 17 in the preparation the corresponding gold( III ) complexes 4, 5 and 6 (Scheme ). Ketone 1 17 and thione 3 16 were previously known as precursors for the synthesis of the organic donors BET‐TTF and DT‐TTF, respectively.…”

Section: Introductionmentioning

confidence: 99%

Gold Complexes with Dithiothiophene Ligands: A Metal Based on a Neutral Molecule

Belo¹,

Alves²,

Lopes³

et al. 2001

Chem. Eur. J.

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114

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The gold complexes n-Bu4N[Au(alpha-tpdt)2] (5), n-Bu4N[Au(dtpdt)2] (4) and n-Bu4N[Au(tpdt)2] (6) based on new dithiothiophene ligands (alpha-tpdt= 2,3-thiophenedithiolate, dtpdt=2,3-dihydro-5,6-thiophenedithiolate and tpdt = 3,4-thiophenedithiolate) have been prepared and characterised. These gold(III) complexes are diamagnetic, but they can be oxidised with iodine to the paramagnetic compounds [Au(alpha-tpdt)2] (8), [Au(dtpdt)2] (7) and n-Bu4N[[Au(tpdt)2]n-2] (9), which were isolated as fine powders and which exhibit paramagnetic susceptibilities that are almost temperature independent with room temperature values of 2.5 x 10(-4), 2.0 x 10(-4) and 5 x 10(-4) emu x mol(-1), respectively. Interestingly, the neutral complex [Au(alpha-tpdt)2] (8) as a polycrystalline sample displays the properties of a metallic system with a room temperature electrical conductivity of 6 S x cm(-1) and a thermoelectric power of 5.5 microVK(-1); this is the first time that this metallic property has been observed in a molecular system based on a neutral species.

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“…The coupling of 4,5-ethylenethio-1,3-dithiol-2-one (1) [5] and 4,5-ethylenedithio-1,3-dithiole-2-thione (2) [8] gave rise to a mixture of the desired donor, ETEDT-TTF, and the symmetrical by-products BET-TTF and BEDT-TTF, which were separated by column chromatography. Because of the formation of these symmetrical derivatives, the yield of ETEDT-TTF is low (18%).…”

Section: Synthesismentioning

confidence: 99%

“…In spite of the poor yields, this cross-coupling route was our preferred choice for obtaining these TTF-based derivatives, since the precursor ketone 1 is easily prepared in gram amounts. [5] In contrast, the corresponding 4,5-ethylenethio-1,3-dithiole-2-thione, that would be expected to function as the precursor of dithiolium ion needed for the more convenient Wittig-like coupling reactions described for the synthesis of disymmetric TTFs, [12] is much more difficult to obtain in good yields. [4,13] …”

Section: Synthesismentioning

confidence: 99%

Novel Dissymmetric Tetrathiafulvalenes as Precursors of Organic Metals: Synthesis, X-ray Crystal Structures, Electrochemical Properties and Study of Their Radical Cations

et al. 2000

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Improved Synthesis of the π-Electron Donor Bis(ethylenethio)tetrathiafulvalene (BET-TTF)

Abstract: Following a three step route, 5,6-dihydrothieno[2,3-d]-1,3-dithiol-2-one (5) was synthesized in gram quantities starting from commercially available reagents. Coupling of 5 with trimethyl phosphite gave the p-donor bis(ethylenethio)tetrathiafulvalene 1 in 80% yield.

Cited by 18 publications

References 12 publications

Organic Spin Ladders from Tetrathiafulvalene (TTF) Derivatives

Organic Spin Ladders from Tetrathiafulvalene (TTF) Derivatives

Gold Complexes with Dithiothiophene Ligands: A Metal Based on a Neutral Molecule

Novel Dissymmetric Tetrathiafulvalenes as Precursors of Organic Metals: Synthesis, X-ray Crystal Structures, Electrochemical Properties and Study of Their Radical Cations

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