Graeme Cooke

Bis(tetrathiofulvalenyl)sulphide [(TTF)2S] : synthesis and x-ray crystal structure

Abstract Bis(tetrathiafulvalenyl)sulphide [(TTF)2S] has been synthesized by reaction of monolithiated TTF with di(phenylsulphonyl)sulphide, and characterised by cyclic voltammetry and single crystal X-ray analysis, which reveals a remarkably close two-dimensional chalcogen network in the solid state. The synthesis of (TTF)2Se, using the selenating reagent di(phenylsulphonyl)diselenide, is also reported. Bis(tetrathiafulvalenyl)sulphide [(TTF)2S] has been synthesised by reaction of monolithiated TTF with di(phenylsulphonyl)sulphide, and characterised by cyclic voltammetry and single crystal X-ray analysis, which reveals a remarkably close two-dimensional chalcogen network in the solid state. The synthesis of (TTF)2Se, using the selenating reagent di(phenylsulphonyl)diselenide, is also reported.

Functionalised tetrathiafulvalene (TTF) systems derived from 4,5-(propylenedithio)-1,3-dithiole units

Abstract A range of functionalised symmetrical and unsymmetrical tetrathiafulvalene (TTF) derivatives containing substituted 4,5-(propylenedithio)-1,3-dithiole units has been prepared. Key half-units are the t-butyldiphenylsilyl-protected 1,3-dithiole derivative 18 and the ketal-protected derivative 32. Self-coupling and cross-coupling reactions of these half-units, with 1,3-dithiole-2-one and -2-thione derivatives 19–22 occurs in the presence of triethylphosphite. After deprotection, TTF derivatives 14, 24, 28, 34 and 40–43, bearing hydroxy or ketone functionality are obtained. Functionalisation of the alcohol group(s) of 14, 24 and 28 has been achieved with acid chlorides and with isocyanates, to give compounds 16, 17, 25, 26 and 29. Cyclic voltammetric studies establish that the new TTF derivatives are efficient π-electron donors; they undergo two reversible, single-electron redox waves. The X-ray crystal structures of 4,5-(2-hydroxypropylenedithio)-1,3-dithiole-2-thione 3 and the ketal-prote

Electrochemical properties of hexadecanoyltetrathiafulvalene Langmuir-Blodgett films

Abstract The electrochemical behaviour of monolayer and multilayer films of hexadecanoyltetrathiafulvalene, deposited on conductive substrates by the Langmuir-Blodgett technique, has been studied by cyclic voltammetry, chronoamperometry and visible/infrared spectroscopy. Monolayer films show stable reversible oxidation to the cation-radical state. However, in thicker structures, the electrochemical response is strongly distorted because of the hindered diffusion of ions.

Synthesis and properties of new functionalized tetrathiafilvalene (ttf) pi-electron donors

The synthesis, solution electrochemistry, and X-ray crystal structures of a wide range of highly-functionalised TTF derivatives are presented.

Conducting langmuir-blodgett films of new amphiphilic tetrathiafulvalene derivatives

Abstract New mono-functionalised, amphiphilic tetrathiafulvalene (TTF) derivatives have been synthesised and shown to form Langmuir-Blodgettt films, some of which are semiconducting ( δ rt = 10 −5 -10 −2 Scm −1 after iodine doping. These layers have been characterised by UV-Visible and IR spectroscopy in the undoped and doped states. X-ray crystal structures of related TTF derivatives substituted with a thioester and a thioamide group are presented.

Synthesis of amphiphilic, mono-functionalised tetrathiafulvalenes; X-ray crystal structure of 4-(6-sromohexanoyl)tetrathiafulvalene

Reaction of monolithiated-tetrathiafulvalene (TTF) has been used in the synthesis of amphiphilic TTF derivatives bearing long chains attached through carbon, silicon, sulphur, selenium, and tellurium atoms; the single crystal X-ray structure of the title compound is described.

Chalcogenation of tetrathiafulvalene (TTF): synthesis of alkylthio-TTF and alkylseleno-TTF derivatives and X-ray crystal structure of ethylenediseleno TTF (EDS-TTF)

The reaction of mono-lithiated tetrathiafulvalene (TTF) with elemental sulfur or elemental selenium at –78 °C yields the transient species TTF-S– Li+ and TTF-Se– Li+, respectively, which have been trapped with a range of alkyl halides to yield new alkylthio- and alkylseleno-TTF derivatives. Reaction of the TTF-thiolate anion with 2-bromoethanol yields 4-(2-hydroxyethylthio)tetrathiafulvalene which is a particularly versatile building block for the synthesis of a range of new mono-functionalised TTF derivatives containing ether, ester, acrylate, urethane and vinylthio groups in the side chain. Onepot syntheses of ethylenedithio-TTF (EDT-TTF) and ethylenediseleno-TTF (EDS-TTF) from TTF are reported. The structure of EDS-TTF has been determined by single crystal X-ray analysis which reveals dimers with molecular planes orthogonal to each other.

4-(N-Methylthioamido)tetrathiafulvalene: a new kappa-phase structure

Tetrathiafulvalenyllithium reacts with N-methylisothiocyanate to afford the title compound 3, which is the first example of a neutral tetrathiafulvalene derivative to form a kappa-phase structure.