Anthracenediylidene derivatives: control of molecular and supramolecular architecture

Abstract

In the context of new π-donor molecules, extended tetrathiafulvalenes have been widely studies for their use as components of electronically conductive charge-transfer materials. In contrast with the planar π -systems, we have focused our attention on extended tetrathiafulvalenes containing a conjugated anthracenyl spacer (anthracenediylidene derivatives). These TTF derivatives adopt a saddle-shaped conformation in the neutral state and a drastic change of conformation occurs upon oxidation to the dication species. Our main objective was to investigate the molecular and supramolecular architecture of these compounds. At the molecular scale, we synthesised cyclophanes by bridging the preformed anthracene tetrathiafulvalene system and studied their redox properties and crystal packing. We developed the chemistry of anthracenediylidene derivatives in order to direct the supramolecular architecture by secondary interactions (hydrogen-bonding, π-π stacking). Finally, we also investigated the incorporation of anthracenediylidene units inside dendritic structures in order to study the highly charged species formed upon oxidation.