abstract
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 pi-extended electroactive frameworks.
keywords
FIELD-EFFECT TRANSISTORS; ELECTRICAL-CONDUCTIVITY; TTF DERIVATIVES; TRANSFORMATION; MOBILITY; PACKING
subject category
Chemistry
authors
Ribeiro, C; Valente, G; Espinosa, M; Silva, RAL; Belo, D; Gil-Guerrero, S; Arisnabarreta, N; Mali, KS; De Feyter, S; Melle-Franco, M; Souto, M
our authors
Groups
G1 - Porous Materials and Nanosystems
G3 - Electrochemical Materials, Interfaces and Coatings
G6 - Virtual Materials and Artificial Intelligence
Projects
CICECO - Aveiro Institute of Materials (UIDB/50011/2020)
CICECO - Aveiro Institute of Materials (UIDP/50011/2020)
Associated Laboratory CICECO-Aveiro Institute of Materials (LA/P/0006/2020)
Redox-active Metal-Organic Frameworks as Electrode Materials for Lithium-Ion Batteries (RedoxMOFs)
Materiais Neutros Solúveis para a Electrónica Molecular (NEUTRABILITY)
Projeto de Investigação Exploratória: Manuel Melle (IF Manuel Melle)
Collaboratory for Emerging Technologies, CoLab (EMERGING TECHNOLOGIES)
acknowledgements
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 (C14/19/079), 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).