Rsc_nj_c1nj20034h 1..7

A chiral tetrathiafulvalene (1) bearing a binaphtholdimethylene moiety on one side, an ethylenedithio substituent on the other side, is prepared from atropoisomeric (R)-, (S)and racemic (R,S)-binaphthol. Its oxidation potential (0.49 V vs. SCE) allows for its oxidation with TCNQF4. Crystal structures of the neutral racemic (R,S)-1 and enantiopure (R)-1 were determined together with those of the enantiopure charge-transfer salts formulated as [(R)-1][TCNQF4] CH2Cl2 and [(S)-1][TCNQF4] CH2Cl2, the first enantiomeric salts of chiral TTFs with axial chirality. Despite the peculiar geometry adopted by the binaphthyl moieties in the constrained ten-membered ring in 1, stacking of the donor molecules is observed, both in the neutral state and in the TCNQF4 charge transfer salts where the (1) + and (TCNQF4) radical species are associated, respectively, into [(1)2] 2+ and [(TCNQF4)2] 2 homodyads, both in their singlet state.