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

Abstract

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)

Self‐Assembled Gelators for Organic Electronics

“…[ [66][67][68][69][70][71][72] Organic Electronics Angewandte Chemie behavior with a conductivity of 10 S cm À1 whereas 31 showed five times less conductivity when doped. The advantage of the hybrid system is that the mixed-valent donor stacks attain a highly conducting b phase without any heat treatment, immediately after doping.…”

Selbstorganisierte Gelbildner für die organische Elektronik

“…Die säulenfçrmigen, p-gestapelten Strukturen verleihen TTF-Materialien eine hohe Elektronenleitfähigkeit. [67] Strom-Spannungs-Messungen dieser Filme ergaben eine Leitfähigkeit innerhalb der Ebene von s rt = 10 À6 S cm À1 , die bei Dotierung mit Iod auf 10 À4 S cm À1 und mit Tetrabutylammoniumperchlorat oder Hexafluorophosphat auf 10 À5 -10 À4 S cm À1 anstieg. [66] Bryce et al stellten erstmals ein leitfähiges TTF-Gel bestehend aus schleuderbeschichteten Filmen von 25 vor.…”

“…Nakamura et al beschrieben ein amphiphiles Bis(TTF)anelliertes makrocyclisches Derivat 28 (Schema 7), das redoxaktive Organogele sowie elektrisch aktive Nanostrukturen wie z. [66][67][68][69][70][71][72] Organische Elektronik Angewandte Chemie akzeptors 2,3,5,6-Tetrafluor-7,7,8,8-tetracyanochinodimethan (F4TCNQ) bildete 29 ein dunkelfarbiges CT-Gel mit einer elektrischen Leitfähigkeit von 5.0 10 À4 S cm À1 . [69] Die beobachtete Leitfähigkeit von 20 nS eines einzelnen Nanopunkts aus chemisch oxidiertem 28 stieg unter Umgebungsbedingungen auf 86 nS infolge des Einflusses von Sauerstoff und/oder Wasser.…”

Tetrathiafulvalene (TTF)-based gelators: Stimuli responsive gels and conducting nanostructures

“…Bryce and his coworkers have recently described the synthesis of thin-film formation of analogous compounds. After oxidative doping, the thin-films show moderate levels of conductivity, indicating that a significant degree of supramolecular order is present [22].…”