Radical Cation Salts Of Tetramethyltetrathiafulvalene (Tm-Ttf) And Tetramethyltetraselenafulvalene (Tm-Tsf) With Chlorocyananilate-Based Anions

Electrocrystallization of tetramethyltetrathiafulvalene (TM-TTF) and tetramethyltetraselenafulvalene (TM-TSF) with chlorocyananilate monoanion or/and tris(chlorocyananilato)ferrate(III) in THF/DCM solvent mixtures yielded a salt formulated as [TM-TTF](4)[K(HClCNAn)(4)] (1) with the former and pi-d hybrid systems, formulated as [TM-TTF](5)[Fe(ClCNAn)3]center dot 2CH(2)Cl(2) (2) and [TMTSF]3[Fe(ClCNAn)3]center dot 0.5CH(2)Cl center dot 2.5H(2)O (3), respectively, with the latter. Compound 1 shows segregation of TM-TTF donor molecules and K(HClCNAn)(4) anionic clusters in the bc plane. The donor molecules are present as mixed-valence dimers and show a beta' packing arrangement. Compounds 2 and 3 consist of hybrid organic/inorganic structures with no segregation of [Fe(ClCNAn)(3)]3- anionic complexes and organic TM-TTF/TM-TSF donors. In the structure of compound 3, TM-TSF dimers are trapped between anilate units of metal complexes of opposite chirality. Furthermore, tetrameric donor motifs and solvent molecules of crystallization complete the structure. Single-crystal conductivity measurements on compounds 1 and 2 show semiconducting behavior with room-temperature conductivity values of 5 x 10(-5) and 2 x 10(-4) 10 S cm(-1) and activation energies of 1960 and 1900 K, respectively. Under high pressure, compound 2 remains a semiconductor, yet its room-temperature conductivity value strongly increases up to 0.2 S cm-1 at 9.8 GPa.