TY - JOUR

T1 - Core carbo‐mer of an Extended Tetrathiafulvalene

T2 - Redox‐Controlled Reversible Conversion to a carbo‐Benzenic Dication

AU - Listunov, Dymytrii

AU - Hammerich, Ole

AU - Caballero‐quintana, Irving

AU - Poater, Albert

AU - Barthes, Cécile

AU - Duhayon, Carine

AU - Larsen, Mie Højer

AU - Maldonado, José‐luis

AU - Ramos‐ortiz, Gabriel

AU - Nielsen, Mogens Brøndsted

AU - Maraval, Valérie

AU - Chauvin, Remi

PY - 2020

Y1 - 2020

N2 - 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.

AB - 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.

U2 - 10.1002/chem.202001700

DO - 10.1002/chem.202001700

M3 - Letter

C2 - 32277543

VL - 26

SP - 10707

EP - 10711

JO - Chemistry: A European Journal

JF - Chemistry: A European Journal

SN - 0947-6539

IS - 47

ER -