Bis (Alkylthio) Tetrathiafulvalenes and a Few of Their Salts

Abstract

Some unsymmetrical bis(alkylthio) tetrathiafulvalenes (n-donors) and a number of their charge transfer complexes and cation radical salts of the type D X (where D=n-donor, X=TCNQ, I 3 ,I~r 2 , PF 6 , mc£o 4 ) have been prepared and sEud~ea.

Electrophilic halogenation of thioethers: 5-chloro- and 5,6-dichloro-5,6-dihydro-1,3-dithiolo[4,5-b][1,4]dithiine-2-one and an efficient synthesis of vinylenedithiotetrathiafulvalene (VDT-TTF)

“…Note that the reported synthesis of VDT-TTF involved the coupling of 4 with 6 in 8% yield and further decarboxylation in 18% yield. 12 Recrystallization from toluene afforded red crystals the X-ray crystal structure of which prove them to be isostructural with the saturated EDT-TTF analogue (Fig. 2).…”

Enantiopure Conducting Salts of Dimethylbis(ethylenedithio)tetrathiafulvalene (DM‐BEDT‐TTF) with the Hexachlororhenate(IV) Anion

“…Moreover, a very interesting ferromagnetic metallic salt has been obtained with ( S , S , S , S )‐TM‐BEDT‐TTF and metal oxalates 5. Following the first reports on TM‐BEDT‐TTF, the dimethylated derivatives of ethylenedithio‐TTF (DM‐EDT‐TTF)6 and BEDT‐TTF (DM‐BEDT‐TTF)7 have been prepared, although in the case of DM‐EDT‐TTF the detailed synthesis of both enantiopure ( S , S ) and ( R , R ) precursors together with their solid‐state structures have been reported only recently by some of us 8. When DM‐EDT‐TTF was electrocrystallized in the presence of the PF 6 – anion, enantiopure semiconducting and racemic metallic phases were obtained 8.…”

Synthesis Strategies and Chemistry of Nonsymmetrically Substituted Tetrachalcogenafulvalenes

“…Another disadvantage of this strategy is the formation of the two symmetric species besides the dissymmetric TTF. 1,16,[98][99][100][101][102][103][104][105][106][107][108] Depending on the relative polarity of the three products obtained as a mixture, the separation of the target TTF can be particularly difficult, as in the case of DMtTSF 18.3 (dimethyltrimethylenetetraselenafulvalene) (Scheme 18a), 98 or, on the contrary, relatively easy, as for the functionalized TTF 18.6 (Scheme 18b) 108 and its sulfur derivative. 109 This is why this strategy has been largely used to prepare functionalized TTF that can be easily separated from the formed mixtures.…”