This work deals with, on the one hand, rigid tetrahiafulvalene (TTF) dimers and the modulation of intramolecular mixed valence and, on the other hand, tris(TTF) derivatives which can auto-assemble to form organogels and fibres that might present supramolecular chirality. In the first part, compounds of the type (TTF)2(XY) (X = PPh, Y = PPh or SiMe2) were synthesised and characterised by X-ray diffraction on single crystal. Their reactivity and coordination chemistry were studied and the intramolecular mixed valence state in the oxidised species was characterised by spectroscopic and theoretic means. In the second part, a new family of compounds which combine electroactive properties thanks to the TTF moieties with a high degree of helical supramolecular organisation is introduced. The compound Ph[CONH-bipy-NHCO-TTF(SEt)2]3 shows good gelation properties in chlorinated solvents. A xerogel composed by two types of fibres was formed and becomes conductive following doping with iodine. The compounds (S)- and (R)-Ph[CONH-bipy-NHCO-TTF(S-2-methylbutyl)2]3, which have chiral isopentyl groups, form fibres that show only one helicity, as showed by optical and scanning electron microscopy studies, by circular dichroism spectroscopy and by molecular mechanics and molecular dynamics calculations.
