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.

Three norbornane fused dihydro-tetrathiafulvalene derivatives which contained the thiol, disulfide and acetylthio functionalities were synthesised. Cyclic voltammetry was used to measure the redox properties of the compounds, which showed that the molecules were able to undergo two reversible, one electron oxidation processes. X-ray structures of all three functionalities were obtained. The three compounds were sublimed onto Au(111) surfaces, and characterised using a number of surface science techniques. Disordered structures are formed initially for all three compounds when adsorbed at room temperature. Following progressive annealing of the substrate, highly ordered adlayer structures are formed that are believed to be bound to the surface via a gold adatom. Van der Waals and hydrogen bonding interactions are shown to play an important role in the formation of these ordered structures. The adsorption of triphenylphosphine sulfide on Au(111) is also investigated, using a combination of RAIRS and STM experiments. Here an extremely ordered (2√3×2√3)R30º structure is formed immediately upon deposition at 298 K. From the experimental data and DFT calculations, the orientation of the molecule is deduced. The attempted synthesis of a thiol functionalised donor-acceptor compound is also described, with a few previously unknown intermediate compounds being synthesised. Finally, a series of four known aryl amidoximes were synthesised. These were subsequently deposited on a Cu(111) crystal and studied using a vibrational spectroscopy. Three of the compounds were found to decompose to varying degrees during the sublimation process. The possible conformations of the amidoxime group on the copper surface are discussed.

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