Direct C−H Arylation of Dithiophene‐Tetrathiafulvalene: Tuneable Electronic Properties and 2D Self‐Assembled Molecular Networks at the Solid/Liquid Interface

• Published in: Chemistry : a European journal 2023-07, Vol.29 (37), p.e202300572-n/a
• Main Authors: Ribeiro, Catarina, Valente, Gonçalo, Espinosa, Miguel, Silva, Rafaela A. L., Belo, Dulce, Gil‐Guerrero, Sara, Arisnabarreta, Nicolás, Mali, Kunal S., De Feyter, Steven, Melle‐Franco, Manuel, Souto, Manuel
• Format: Article
• Language: English
• Subjects: Chemical bonds; Chemistry; Construction; cyclic voltammetry; DFT calculations; dithiophene-tetrathiafulvalene; Electronics; Graphite; Molecular electronics; Redox properties; Scanning tunneling microscopy; scanning tunnelling microscopy (STM); self-assembled molecular networks; Self-assembly; Spectroscopy
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202300572

Tetrathiafulvalene is among the best known building blocks in molecular electronics due to its outstanding electron‐donating and redox properties. Among its derivatives, dithiophene‐tetrathiafulvalene (DT‐TTF) has attracted considerable interest in organic electronics, owing to its high field‐effect mobility. Herein, we report the direct C−H arylation of DT‐TTF to synthesise mono‐ and tetraarylated derivatives functionalised with electron‐withdrawing and electron‐donating groups in order to evaluate their influence on the electronic properties by cyclic voltammetry, UV‐vis spectroscopy and theoretical calculations. Self‐assembly of the DT‐TTF‐tetrabenzoic acid derivative was studied by using scanning tunnelling microscopy (STM) which revealed the formation of ordered, densely packed 2D hydrogen‐bonded networks at the graphite/liquid interface. The tetrabenzoic acid derivative can attain a planar geometry on the graphite surface due to van der Waals interactions with the surface and H‐bonding with neighbouring molecules. This study demonstrates a simple method for the synthesis of arylated DT‐TTF derivatives towards the design and construction of novel π‐extended electroactive frameworks. Herein we report the direct C−H arylation of dithiophene‐tetrathiafulvalene (DT‐TTF) to synthesise mono‐ and tetraarylated derivatives functionalised with different groups. The self‐assembly of DT‐TTF‐tetrabenzoic acid derivative was studied by using scanning tunnelling microscopy, which revealed the formation of ordered, densely packed 2D hydrogen‐bonded networks at the graphite/liquid interface.