Direct C-H Arylation of Dithiophene-Tetrathiafulvalene: TuneableElectronic Properties and 2D Self-Assembled Molecular Networksat the Solid/Liquid Interface


Tetrathiafulvalene is among the most well-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 theelectronic properties by cyclic voltammetry, UV-vis spectroscopy and theoretical calculations. Self-assembly of the DT-TTF-tetrabenzoic acid derivative was studied 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 forthe construction of novel π-extended electroactive frameworks.


Gonçalo Valente, Catarina Ribeiro, Miguel Espinosa,Rafaela A. L. Silva, Dulce Belo, Sara Gil-Guerrero, NicolásArisnabarreta, Kunal S. Mali, Steven De Feyter, ManuelMelle-Franco, and Manuel Souto

our authors


This work has received funding from the European Research Council (ERC) under the European Union’s Horizon Europe Framework Programme (ERC-2021-Starting Grant, grant agreement no. 101039748-ELECTROCOFS). This work was developed within the scope of the project CICECO-Aveiro Institute of Materials, Grants UIDB/50011/2020, UIDP/50011/2020 & LA/P/0006/2020, financed by national funds through the FCT/MCTES (PIDDAC). We thank FCT for funding the projects PTDC/QUI-ELT/2593/2021, PTDC/QUI-QIN/29834/2017 and IF/00894/2015. N.A, K.S.M and S.D.F acknowledge the financial support from KU Leuven – Internal Funds, a postdoctoral mandate Internal Funds, as well as FWO project 12ZS623N. We also thank the advanced computing project 2021.09622.CPCA granting access to the Navigator cluster at LCA-UC. G. V. is grateful to FCT for a Ph.D. grant (2020.08520.BD).

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