Arborol-Functionalised Tetrathiafulvalene Derivatives: Synthesis and Thin-Film Formation

• Published in: European journal of organic chemistry 2003-09, Vol.2003 (18), p.3562-3568
• Main Authors: Gall, Thierry Le, Pearson, Christopher, Bryce, Martin R., Petty, Michael C., Dahlgaard, Henriette, Becher, Jan
• Format: Article
• Language: English
• Subjects: Arborol; Redox activity; Tetrathiafulvalene; Thin films
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.200300286

The syntheses of a series of novel tetrathiafulvalene derivatives substituted with four side‐chains terminating in hydrophilic amidoalcohol (arborol) groups are reported, for example the tetrathiafulvalene derivative 15. Some of these arborol derivatives formed thin films by spin‐coating from methanol solution onto solid supports such as glass, ITO‐coated glass and gold. The quality of the films improved markedly with an increasing number of alcohol substituents at the periphery of the molecule. Optical absorption spectroscopy showed that oxidative doping of these films could be achieved chemically and electrochemically. The observation of low‐energy bands in the UV/Vis absorption spectra (λmax = 820 nm tailing to ca. 1300 nm) and the moderate levels of conductivity (σrt ≈︁ 10−4 S cm−1) in these doped films strongly suggest that a significant degree of supramolecular order is present, with π‐π stacking of the TTF cores. To the best of our knowledge this is the first time that semiconducting behaviour has been achieved in molecular arborol systems that possess an electroactive core unit. This work offers the prospect of using spin‐coated films of TTF‐arborols as semiconducting charge‐transport layers in optoelectronic devices. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)