Synthesis of a new extended π-donor with 1,4-oxathiane annulation

Hellberg, Jonas; Balodis, K. A.; Moge, Mikael; Korall, Peter; vonSchütz, J-U.

doi:10.1039/a603837i

“…In the synthesis of BDDT-TTF ( 6 ) by phosphite-coupling reaction between 17 and 18 , it has been reported that the formation of two diastereomers of 6 can be confirmed by a 1 H NMR spectrum study . On the other hand, the assignment for the two diastereomers of 7 could not be clearly made on the basis of 1 H NMR analysis due to their insolubility in appropriate solvents (e.g., CDCl 3 , THF- d 8 , and CDCl 3 −CS 2 ) for the analysis; however, it is presumed that the two diastereomers were formed in the course of the self-coupling reaction, since the difference in conformational energy between two diastereomers of 7 , similarly to those of 6 , does not seem to be large enough to enable the exclusive formation of one diastereomer …”

Section: Resultsmentioning

confidence: 99%

“…Therefore, one synthetic method for the construction of new TTF donors leading to conducting salts with enhanced dimensionality of conduction might be the addition of another heterocycle onto the existing one or both outer rings in the known heterocycle-fused TTF derivatives, and to this end, the bis(dioxane)-fused BEDT-TTF derivative [BDDT-TTF ( 6 )] has been already synthesized . Further appearance of such a π-electron donor bearing extended substituents by the σ-bond framework on the periphery of the TTF core would be of interest in preparation of new molecular-based conductors 1 …”

Section: Introductionmentioning

confidence: 99%

New Tetrathiafulvalene Donors with Extended Peripheral Substituents by Addition of Heterocycles: Synthesis, Properties, and Molecular Structures

Yamada

¹

,

Tanaka

²

,

Segawa

³

et al. 1998

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Syntheses of the bis(heterocycle)-fused bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) derivatives 7 and 8, the heterocycle-fused BEDT-TTF, methylenedithio(ethylenedithio)tetrathiafulvalene (MET), and ethylenedithiotetrathiafulvalene derivatives 9-11, and the 1,3-dioxolane derivative of MET 12a and its analogues 12b-d are described. The heterocycle-fused ketones 17 and 19 with cis ring fusions could be prepared by the BF 3 -promoted reaction of tin dithiolate 13 with dihaloheterocycles 15 and 16 in good yields, respectively, and served as key intermediates for the (RO) 3 Pand/or Me 3 Al-promoted coupling syntheses of these new tetrathiafulvalene donors 7-12. Further, the electrochemical properties of new donors 8-12 by the use of cyclic voltammetry and the molecular structures of 9a, 10a, 11, and 12a by X-ray crystallographic analyses are also reported.

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“…Syntheses of the ''all sulfur'' analogues of 128 and 129 have been reported, 68 and a ''mixed system'' has been prepared from 2,3-dihydro-1,4-oxathiine, but the relative positions of the O and S atoms in the outer rings lead to a larger mixture of stereoisomers. 72 ET donors fused to one or two tetrahydrofuran rings have been prepared from 2,5-dihydrofuran, and a range of radical cation salts characterized. 73…”

Section: Hydroxy and Ether Functionalised Et Derivativesmentioning

confidence: 99%

Substituted BEDT-TTF derivatives: synthesis, chirality, properties and potential applications

Wallis

¹

,

Griffiths

²

2005

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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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“…Syntheses of the "all sulfur" analogues of 128 and 129 have been reported, 68 and a "mixed system" has been prepared from 2,3-dihydro-1,4-oxathiine, but the relative positions of the O and S atoms in the outer rings leads to a larger mixture of stereoisomers. 72 ET donors fused to one or two tetrahydrofuran rings have been prepared from 2,5-dihydrofuran, and a range of radical cation salts characterized. …”

Section: Hydroxy and Ether Functionalised Et Derivativesmentioning

confidence: 99%

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

Wallis

¹

,

Griffiths

²

2005

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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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Synthesis of a new extended π-donor with 1,4-oxathiane annulation

Cited by 15 publications

References 7 publications

New Tetrathiafulvalene Donors with Extended Peripheral Substituents by Addition of Heterocycles: Synthesis, Properties, and Molecular Structures

New Tetrathiafulvalene Donors with Extended Peripheral Substituents by Addition of Heterocycles: Synthesis, Properties, and Molecular Structures

Substituted BEDT-TTF derivatives: synthesis, chirality, properties and potential applications

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

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