S-position isomers of BEDT-TTF and EDT-TTF: Synthesis and influence of outer sulfur atoms on the electrochemical properties and crystallographic network of related organic metals

The synthesis and characterization of new modified tetrathiafulvalenes (TTF ), the S-position isomers of BEDT-TTF and EDT-TTF. are described. The synth etic strategy presented in this work is based on an efficient and unprecede nted two-step sequence for the conversion of a vicinal bis(hydroxymethyl) f unctionality into a disulfide ring. Different routes are discussed in terms of efficiency for the synthesis of the symmetric S-position isomer of BEDT -TTF and that of EDT-TTF. Their electrochemical properties are combined wit h data obtained from UV/Vis spectroscopy and orbital calculations, and the electronic influence of peripheral sulfur atoms on the neutral and oxidized species is discussed. The introduction of these outer sulfur atoms at the periphery of the TTF core gives rise to specific intermolecular S . . .S in teractions in the corresponding organic materials. Crystallographic studies of radical cation salts synthesized upon electrocrystallization clearly sh owed that the network obtained is dictated by the outer sulfur atoms, which are responsible for a characteristic and unprecedented "windmill" array.