Synthesis and X-ray crystal structures of radical cation salts of benzo-TTF derivatives with Cu2Cl62−, CuCl42− and ClO4− anions

The reactions of CETBz-TTF (4,5-bis(cyanoethylthio)benzo-tetrathiafulvalene), CESBz-TTF (4,5-bis(cyanoethylseleno)benzo-tetrathiafulvalene) and TCE-TTF (tetrakis(2′-cyanoethylthio)tetrathiafulvalene) with copper(II) salts such as CuCl·2H2O or Cu(ClO4)2·6H2O generate paramagnetic dimer of Cu(II) complex anion (CETBz-TTF)2[Cu2Cl6(H2O)2], tetrachlorate Cu(II) salt (CETBz-TTF)2CuCl4 and perchlorate radical cation salts (CETBz-TTF)ClO4·CH3CN, (CESBz-TTF)ClO4·2H2O and (TCE-TTF)ClO4. Synthesis and X-ray crystal structures of all the salts are presented. As expected from the crystal structures, paramagnetic behaviour is observed for all the salts.