Tetrathiafulvaleneand TetramethyltetraselenafulvaleneSalts with [M(dcdmp) 2 ] Anions (M = Au, Cu, and Ni): HighConductivity and Unusual Stoichiometries

Four new charge transfer salts based on TTF or TMTSF (TTF= tetrathiafulvalene, TMTSF= tetramethyltetraselenafulvalene) donors and transition metal complexes [M(dcdmp)2] (dcdmp= 2,3 dicyano 5,6 dimercaptopyrazine), TMTSF5[Cu(dcdmp)2]4 (1), (TMTSF)2[Ni(dcdmp)2] (2) and (TTF)7[M(dcdmp)2]6 (M=Au (3) and Cu (4)), were prepared by electrocrystallization. These compounds are characterized by a rich variety of crystal structures with unusual donor:acceptor stoichiometries. In spite of the uncommon structural types observed these salts can be highly conducting. Compound 1 crystallizes with segregated TMTSF stacks, showing ID metallic properties with a room temperature conductivity of 134 S/cm. Compound 2 crystalizes in an out-of-registry mixed columns arrangement of donor dimers and acceptors. Compound 3 and 4 appear in single crystal X-ray diffraction as isostructural and composed of columns of TTF hexamers that are disrupted by a single TTF layer and surrounded by [M(dcdmp)2]- monoanionic pairs, aligning perpend...