Efficient synthesis of brominated tetrathiafulvalene (TTF) derivatives: solid-state structure and electrochemical behaviour

Alberola, Antonio; Collis, Rebecca J.; Garcı́a, Felipe; Howard, Ruth E.

doi:10.1016/j.tet.2006.06.006

Cited by 9 publications

(7 citation statements)

References 17 publications

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“…The neutral EDT-TTF-I 2 molecule was prepared as previously described (Domercq et al, 2001), and recrystallized by slow evaporation from a CS 2 solution, to provide crystals suitable for X-ray diffraction experiments. Since this reported synthetic procedure provides EDT-TTF-I 2 only in low yield, we also explored an alternative synthetic path that had been used for the analogous dibromo derivative (Batsanov et al, 2001;Alberola et al, 2006). Full details of this synthesis are described in the supporting information, 1 together with the crystal structure of one of the synthesis intermediates, [NC(CH 2 ) 2 S] 2 TTFI 2 .…”

Section: Methodsmentioning

confidence: 99%

C—I...NC halogen bonding in two polymorphs of the mixed-valence 2:1 charge-transfer salt (EDT-TTF-I₂)₂(TCNQF₄), with segregatedversusalternated stacks

Lieffrig¹,

Jeannin²,

Vacher³

et al. 2014

Acta Crystallogr Sect B

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Oxidation of diiodoethylenedithiotetrathiafulvalene (EDT-TTF-I2), C8H4I2S6, with the strong oxidizer tetrafluorotetracyanoquinodimethane (TCNQF4), C12F4N4, affords, depending on the crystallization solvent, two polymorphs of the 2:1 charge-transfer salt (EDT-TTF-I2)2(TCNQF4), represented as D2A. In both salts, the TCNQF4 is reduced to the radical anion state, and is associated through short C-I...NC halogen bonds to two EDT-TTF-I2 molecules. The two polymorphs differ in the solid-state association of these trimeric D-A-D motifs. In polymorph (I) the trimeric motif is located on an inversion centre, and hence both EDT-TTF-I2 molecules have +0.5 charge. Together with segregation of the TTF and TCNQ derivatives into stacks, this leads to a charge-transfer salt with high conductivity. In polymorph (II) two crystallographically independent EDT-TTF-I2 molecules bear different charges, close to 0 and +1, as deduced from an established correlation between intramolecular bond lengths and charge. Overlap interactions between the halogen-bonded D(0)-A-∙D+∙ motifs give rise, in a perpendicular direction, to diamagnetic A2(2-) and D(0)-D2(2+)-D(0) entities, where the radical species are paired into the bonding combination of respectively the acceptor LUMOs and donor HOMOs. The strikingly different solid-state organization of the halogen-bonded D-A-D motifs provides an illustrative example of two modes of face-to-face interaction between π-type radicals, into either delocalized, uniform chains with partial charge transfer and conducting behaviour, or localized association of radicals into face-to-face A2(2-) and D2(2+) dyads.

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Section: Methodsmentioning

confidence: 99%

C—I...NC halogen bonding in two polymorphs of the mixed-valence 2:1 charge-transfer salt (EDT-TTF-I₂)₂(TCNQF₄), with segregatedversusalternated stacks

Lieffrig¹,

Jeannin²,

Vacher³

et al. 2014

Acta Crystallogr Sect B

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“…The cross-coupling reaction of 4,5-dibromo-1,3-dithiol-2-thione 87 with 4,5-ethylenedithio-1,3-diselenole-2-one 34 afforded 4,5-dibromo-4’,5’-ethylenedithiodiselenadithiafulvalene 88 in 80% yield ( Scheme 28 ) [ 77 ]. Compound 88 exhibited electron-donating properties.…”

Section: The 14-diselenafulvene and 1458-tetraselenafulvalene Derivat...mentioning

confidence: 99%

Recent Advances in Design and Synthesis of Diselenafulvenes, Tetraselenafulvalenes, and Their Tellurium Analogs and Application for Materials Sciences

Махаева¹,

Амосова²,

Потапов³

2022

Molecules

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The first organic metals were obtained based on tetrathiafulvalene. The most significant advance in the field of organic metals was the discovery of superconductivity. The first organic superconductors were obtained based on tetramethyltetraselenafulvalene. These facts demonstrate great importance of tetraselenafulvalenes and their precursors, diselenafulvenes, for materials sciences. Derivatives of 1,4-diselenafulvene and 1,4,5,8-tetraselenafulvalene are useful building blocks for organic synthesis and donor units for the preparation of charge-transfer complexes and radical ion salts, the construction of organic metals, superconductors, organic Dirac materials, semiconductors, ferromagnets, and other conductive materials. This review covers the literature on the design, synthesis, and application of 1,4,5,8-tetraselenafulvalenes and 1,4-diselenafulvenes and their tellurium analogs over the past 15–20 years. These two classes of compounds are interconnected, since the main part of methods for the synthesis of tetraselenafulvalenes is based on the diselenafulvene derivatives as starting compounds. Special attention is paid to the development of novel efficient synthetic approaches to these classes of compounds. Conducting properties and distinguishing features of materials based on tetraselenafulvalenes and their tellurium analogs as well as examples of materials with high conductivity are discussed.

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“…For general background to the applications of halogenated 1,3-dithiole-2-thiones, see: Alberola et al 2006;Batsanov et al (2001); Jeppesen et al (2004); Segura & Martin (2001); Wang et al (1995). For a related structure, see: Zhao et al (2008).…”

Section: Related Literaturementioning

confidence: 99%

“…Tetrathiafulvalene (TTF) and its derivatives have attracted great interest for their high electronic conductivity, superconductivity as well as supramolecular features (Segura & Martin, 2001;Jeppesen et al, 2004). The attachment of halogen atoms to TTF framework reduces the π-electron donating ability and this effect is additive with an increasing number of halogens on the TTF system (Wang et al, 1995), As important precursors to the halogenated TTF derivatives, 1,3-dithiole-2-(thi)ones involving bromine groups have also attracted attention (Batsanov et al, 2001;Alberola et al, 2006). We describe here the synthesis and structure of a novel 4-bromo-5-[(2-bromoethyl)sulfanyl]-1,3-dithiole-2-thione compound, (I) ( Fig.…”

Section: S1 Commentmentioning

confidence: 99%

4-Bromo-5-[(2-bromoethyl)sulfanyl]-1,3-dithiole-2-thione

et al. 2009

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The title compound, C5H4Br2S4, consists of a statistically planar, 4-bromo-1,3-dithiole-2-thione unit [maximum deviation from the ring plane 0.001 (2) Å], with a bromoethylsulfanyl substituent in the 5-position. In the crystal structure, weak intermolecular S⋯S [3.438 (15) and 3.522 (15) Å] and S⋯Br [3.422 (14) and 3.498 (14) Å] interactions generate a three-dimensional supramolecular architecture.

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Efficient synthesis of brominated tetrathiafulvalene (TTF) derivatives: solid-state structure and electrochemical behaviour

Cited by 9 publications

References 17 publications

C—I...NC halogen bonding in two polymorphs of the mixed-valence 2:1 charge-transfer salt (EDT-TTF-I₂)₂(TCNQF₄), with segregatedversusalternated stacks

C—I...NC halogen bonding in two polymorphs of the mixed-valence 2:1 charge-transfer salt (EDT-TTF-I₂)₂(TCNQF₄), with segregatedversusalternated stacks

Recent Advances in Design and Synthesis of Diselenafulvenes, Tetraselenafulvalenes, and Their Tellurium Analogs and Application for Materials Sciences

4-Bromo-5-[(2-bromoethyl)sulfanyl]-1,3-dithiole-2-thione

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Efficient synthesis of brominated tetrathiafulvalene (TTF) derivatives: solid-state structure and electrochemical behaviour

Cited by 9 publications

References 17 publications

C—I...NC halogen bonding in two polymorphs of the mixed-valence 2:1 charge-transfer salt (EDT-TTF-I2)2(TCNQF4), with segregatedversusalternated stacks

C—I...NC halogen bonding in two polymorphs of the mixed-valence 2:1 charge-transfer salt (EDT-TTF-I2)2(TCNQF4), with segregatedversusalternated stacks

Recent Advances in Design and Synthesis of Diselenafulvenes, Tetraselenafulvalenes, and Their Tellurium Analogs and Application for Materials Sciences

4-Bromo-5-[(2-bromoethyl)sulfanyl]-1,3-dithiole-2-thione

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C—I...NC halogen bonding in two polymorphs of the mixed-valence 2:1 charge-transfer salt (EDT-TTF-I₂)₂(TCNQF₄), with segregatedversusalternated stacks

C—I...NC halogen bonding in two polymorphs of the mixed-valence 2:1 charge-transfer salt (EDT-TTF-I₂)₂(TCNQF₄), with segregatedversusalternated stacks