New precursors for preparing organic conducting materials: synthesis of (R)-hydroxymethylbis(ethylenedithio)tetrathiafulvalene, and the ring expansion of a cyclic sulfate ester

Leurquin, Fabien; Öztürk, Turan; Pilkington, Melanie; Wallis, John D.

doi:10.1039/a704364c

Cited by 31 publications

(10 citation statements)

References 13 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The O-benzoyl analogue rearranges quantitatively to the six-membered cyclic sulfate ester 112, with intramolecular ring opening of the cyclic sulfate ester as the likely starting point (Scheme 16). 62 Cycloaddition reactions of trithione 7 with but-3-en-1-ol and cis-or trans-but-2-en-1,4-diol have led to the hydroxyethyl 24,63 and cis-60 and trans 24 -bis(hydroxymethyl) thiones 113-115 respectively. After O-protection with acetyl or tertbutyldiphenylsilyl groups, the synthetic plan outlined in Scheme 15 led to hydroxyethyl-ET (HEET) 116, 24,63 and the cis and trans isomers of bis(hydroxymethyl)ET 117-118.…”

Section: Hydroxy and Ether Functionalised Et Derivativesmentioning

confidence: 99%

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

Wallis

Griffiths

2005

J. Mater. Chem.

Self Cite

View full text Add to dashboard Cite

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

show abstract

Section: Hydroxy and Ether Functionalised Et Derivativesmentioning

confidence: 99%

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

Wallis

Griffiths

2005

J. Mater. Chem.

Self Cite

View full text Add to dashboard Cite

show abstract

“…Although there is a relatively large number of chiral TTF derivatives, only a few conducting properties for chiral cation salts have been so far reported, for those based upon tetramethyl- 4 [ 11 – 15 ], 5 [ 7 – 8 ], 6 [ 9 – 10 ], and X-dimethyl-(ethylenedithio)tetrathiafulvalene (X = ethylenedithio [ 16 – 17 ], ethylenedioxy [ 18 ], and pyrazino [ 19 ]), due to the difficulty of chiral-crystal growth. In order to improve the crystallinity, the inclusion of hydroxy groups in the BEDT-TTF molecule has been postulated to produce hydrogen bonding interactions between electron-donor molecules, electron-acceptor molecules, and anions in the subsequent radical cation salts [ 20 – 22 ]. This may lead to improved order in the crystalline state, which in turn may help the observation of physical properties of the salts.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of racemic and chiral BEDT-TTF derivatives possessing hydroxy groups and their achiral and chiral charge transfer complexes

Krivickas

Hashimoto

Yoshida

et al. 2015

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

SummaryChiral molecular crystals built up by chiral molecules without inversion centers have attracted much interest owing to their versatile functionalities related to optical, magnetic, and electrical properties. However, there is a difficulty in chiral crystal growth due to the lack of symmetry. Therefore, we made the molecular design to introduce intermolecular hydrogen bonds in chiral crystals. Racemic and enantiopure bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) derivatives possessing hydroxymethyl groups as the source of hydrogen bonds were designed. The novel racemic trans-vic-(hydroxymethyl)(methyl)-BEDT-TTF 1, and racemic and enantiopure trans-vic-bis(hydroxymethyl)-BEDT-TTF 2 were synthesized. Moreover, the preparations, crystal structure analyses, and electrical resistivity measurements of the novel achiral charge transfer salt θ21-[(S,S)-2]3[(R,R)-2]3(ClO4)2 and the chiral salt α’-[(R,R)-2]ClO4(H2O) were carried out. In the former θ21-[(S,S)-2]3[(R,R)-2]3(ClO4)2, there are two sets of three crystallographically independent donor molecules [(S,S)-2]2[(R,R)-2] in a unit cell, where the two sets are related by an inversion center. The latter α’-[(R,R)-2]ClO4(H2O) is the chiral salt with included solvent H2O, which is not isostructural with the reported chiral salt α’-[(S,S)-2]ClO4 without H2O, but has a similar donor arrangement. According to the molecular design by introduction of hydroxy groups and a ClO4 − anion, many intermediate-strength intermolecular hydrogen bonds (2.6–3.0 Å) were observed in these crystals between electron donor molecules, anions, and included H2O solvent, which improve the crystallinity and facilitate the extraction of physical properties. Both salts are semiconductors with relatively low resistivities at room temperature and activation energies of 1.2 ohm cm with E a = 86 meV for θ21-[(S,S)-2]3[(R,R)-2]3(ClO4)2 and 0.6 ohm cm with E a = 140 meV for α'-[(R,R)-2]2ClO4(H2O), respectively. The variety of donor arrangements, θ21 and two kinds of α’-types, and their electrical conductivities of charge transfer complexes based upon the racemic and enantiopure (S,S)-2, and (R,R)-2 donors originates not only from the chirality, but also the introduced intermolecular hydrogen bonds involving the hydroxymethyl groups, perchlorate anion, and the included solvent H2O.

show abstract

“…5 To provide further materials for investigation we and others have prepared a range of enantiopure organosulfur donors, e.g. 4-10 [6][7][8][9][10][11][12] and have reported some of their radical cation salts. 7,8,10,11 In particular, Avarvari, Rikken et al have shown that the metallic 2 : 1 salts of R,R or S,S-8 with ClO 4…”

mentioning

confidence: 99%

Contrasting crystal packing arrangements in triiodide salts of radical cations of chiral bis(pyrrolo[3,4-d])tetrathiafulvalenes

et al. 2015

Self Cite

View full text Add to dashboard Cite

Crystal structures of six 1:1 triiodide salts of a series of enantiopure bis(pyrrolo[3,4-d])TTF derivatives, the first structures of radical cation salts reported for this bis(pyrrolo) donor system, show three different arrangements of triiodide ions, organised either in head-to-tail pairs, in infinite lines, or in a castellated arrangement. The complex crystal structures, obtained by electrocrystallisation, are influenced by the presence of solvent, for example changing an ABCABC packing arrangement to ABAB with inclusion of THF, as well as by the size of the chiral side chain.

show abstract

New precursors for preparing organic conducting materials: synthesis of (R)-hydroxymethylbis(ethylenedithio)tetrathiafulvalene, and the ring expansion of a cyclic sulfate ester

Cited by 31 publications

References 13 publications

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

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

Synthesis of racemic and chiral BEDT-TTF derivatives possessing hydroxy groups and their achiral and chiral charge transfer complexes

Contrasting crystal packing arrangements in triiodide salts of radical cations of chiral bis(pyrrolo[3,4-d])tetrathiafulvalenes

Contact Info

Product

Resources

About