Electrical and Spectroscopic Properties of TTF and TSF Salts with Tetrahalogenozinc(II) and ‐cadmium(II) Anions

Several tetrathiafulvalene (TTF) and tetraselenafulvalene (TSF) salts of tetrahalogenozinc(II) and ‐cadmium(II) anions Dx[MX4] (D = TTF or TSF; M = Zn and Cd; X = Cl, Br, and I; x= 2.0‐6.6) have been prepared by the reaction of [TTF]3[BF4]2or [TSF]3[BF4]2with [NEt4]2[MX4] in acetonitrile and by the electrolysis of TTF or TSF in acetonitrile containing [NEt4]2[MBr4]. Electrical resistivities of these salts measured for compressed pellets fall in the range 1 × (101–107) Ω cm at 25 °C; the value decreases with increasing bulkiness of the anions: [MCl4]2–> [MBr4]2−> [MI4]2−. Stackings and electronic states of TTF and TSF molecules are discussed on the basis of electronic reflectance, ESR, IR, and Raman spectra.