Geometrically Constrained Tetrathiafulvalenophanes: Synthesis and Characterization

The synthesis of tetrathiafulvalenophanes 4b, 4c, 5, 9, and 10 employing two fundamentally different strategies is reported. Macrocycle 9 was obtained as a mixture of cis and trans isomers and was crystallized to afford two distinct crystals types: a red type consisting of the cis isomer and a yellow type consisting of the trans isomer. The crystal structures of cis-9 and trans-9, determined by X-ray diffraction, revealed that the cis-form possesses a planar TTF moiety while the trans-form has a distorted TTF unit. The electrochemical properties of the new tetrathiafulvalenophanes are reported.