Core carbo‐mer of an Extended Tetrathiafulvalene: Redox‐Controlled Reversible Conversion to a carbo‐Benzenic Dication

carbo‐Benzene is an aromatic molecule devised by inserting C2 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 electro...

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Published in:Chemistry : a European journal 2020-08, Vol.26 (47), p.10707-10711
Main Authors: Listunov, Dymytrii, Hammerich, Ole, Caballero‐Quintana, Irving, Poater, Albert, Barthes, Cécile, Duhayon, Carine, Larsen, Mie Højer, Maldonado, José‐Luis, Ramos‐Ortiz, Gabriel, Nielsen, Mogens Brøndsted, Maraval, Valérie, Chauvin, Remi
Format: Article
Language:English
Subjects:
Absorption spectroscopy
alkyne
Aromaticity
Benzene
carbo-mer
Chemical bonds
Chemical reduction
Chemical Sciences
Chemistry
Computer applications
Coordination chemistry
Crystallography
Density functional theory
Electrochemistry
extended tetrathiafulvalene
Hydrocarbons
Oxidation
Pyrolytic graphite
quinoid
Radicals
redox behavior
Scanning tunneling microscopy
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Summary:carbo‐Benzene is an aromatic molecule devised by inserting C2 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. Outreach: The family of extended tetrathiafulvalene (TTF) molecules is expanded to core‐carbo‐meric versions through a carbo‐p‐quinoidal representative, whose redox pro‐aromatic C18 core is shown to be compatible with stability, supramolecular 2D assembly, and reversible redox properties.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.202001700