Tetrathiafulvalenoparacyclophanes

In the “metallic” conducting 1:1 complex of tetrathiafulvalene (TTF) and tetracyanoquinodimethane (TCNQ), donor and acceptor molecules form separate stacks in the crystal. In order to enforce other TTF/TCNQ arrangements by altering the molecular architecture the phane-like bridged TTF-paracyclophanes (1), n = 3, and (2) were first synthesized. To do this a novel reaction sequence had to be developed which also facilitated synthesis of the tetrathiafulvalenophanes (3)/(4) (and the corresponding [2.2]-derivatives). (3)/(4) and TCNQ form a 1:4 complex having a conductivity of σ = 5 × 10−3 to 10−2 [Ω cm]−1 (single crystal, long axis, 300 K).