Core carbo-mer of an Extended Tetrathiafulvalene: Redox-Controlled Reversible Conversion to a carbo-Benzenic Dication |
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| Authors: | Dr Dymytrii Listunov Prof Ole Hammerich Irving Caballero-Quintana Dr Albert Poater Cécile Barthes Dr Carine Duhayon Dr Mie Højer Larsen Dr José-Luis Maldonado Dr Gabriel Ramos-Ortiz Prof Mogens Brøndsted Nielsen Dr Valérie Maraval Prof Remi Chauvin |
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| Institution: | 1. LCC-CNRS, Université de Toulouse, CNRS, UPS, Toulouse, France;2. Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 Copenhagen, Denmark;3. Centro de Investigaciones en Óptica A.P. 1-948, 37000 León, Gto., Mexico;4. Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, c/ Maria Aurèlia Capmany, 69, 17003 Girona, Catalonia, Spain;5. School of Biomedical Sciences, Huaqiao University, Xiamen, 361021 P. R. China |
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| Abstract: | 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. |
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| Keywords: | alkyne carbo-mer extended tetrathiafulvalene quinoid redox behavior |
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