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Core carbo ‐mer of an Extended Tetrathiafulvalene: Redox‐Controlled Reversible Conversion to a carbo ‐Benzenic Dication
Author(s) -
Listunov Dymytrii,
Hammerich Ole,
CaballeroQuintana Irving,
Poater Albert,
Barthes Cécile,
Duhayon Carine,
Larsen Mie Højer,
Maldonado JoséLuis,
RamosOrtiz Gabriel,
Nielsen Mogens Brøndsted,
Maraval Valérie,
Chauvin Remi
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202001700
Subject(s) - tetrathiafulvalene , dication , highly oriented pyrolytic graphite , molecule , chemistry , redox , cyclic voltammetry , density functional theory , photochemistry , aromaticity , scanning tunneling microscope , benzene , crystallography , electrochemistry , materials science , computational chemistry , nanotechnology , inorganic chemistry , organic chemistry , electrode
carbo ‐Benzene is an aromatic molecule devised by inserting C 2 units within each C−C bond of the benzene molecule. By integrating the corresponding carbo ‐quinoid core as bridging unit in a π‐extended tetrathiafulvalene (exTTF), it is shown that a carbo ‐benzene ring can be reversibly formed by electrochemical reduction or oxidation. The so‐called carbo ‐exTTF molecule was thus experimentally prepared and studied by UV–visible absorption spectroscopy and cyclic voltammetry, as well as by X‐ray crystallography and by scanning tunneling microscopy (STM) on a surface of highly oriented pyrolytic graphite (HOPG). The molecule and its oxidized and reduced forms were subjected to a computational study at the density functional theory (DFT) level, supporting carbo ‐aromaticity as a driving force for the formation of the dication, radical cation, and radical anion. By allowing co‐planarity of the dithiolylidene rings and carbo ‐quinoidal core, carbo ‐exTTFs present a promising new class of redox‐active systems.