Efficient synthesis of ethylenedioxotetrathiafulvalene(EDO-TTF) and analysis of the role of S...S van der Waals interactions in the crystal chemistry of neutral TTF derivatives

摘要

An efficient synthesis of ethylenedioxotetrathiafulvalene (EDO-TTF), a non-symmetrically substituted tetrathiafulvalene, is described together with that of the corresponding acid and amide derivatives, EDO-TTF-CO_2H and EDO-TTF-CONRR (R,R' = H,Me), whose redox potentials are also reported. The X-ray crystal structures of EDO-TTF and EDO-TTF-CO_2H have bee ndetermined and the solid state arrangement of the two compounds compared with that of other TTF derivatives,such as EDT-TTF,EDT-TTF-CO_2H and the parent symmetrically substituted BEDT-TTF and BEDO-TTF, revealing that a large number of sulfur atoms in the molecule stabilizes a face-to-face diad association through S...S van der Waals interactions with a characteristic bond-over-ring overlap while an increased number of light (C,H,O)atoms, as found in BEDO-TTF, leads to solid state associations reminiscent of the herring-bone pattern described for the smallest polynuclear aromatic hydrocarbons