Electronic interactions in a new pi-extended tetrathiafulvalene dimer.

Diaz, M.C.; Illescas, B.M.; Martin, N.; Perepichka, I.E.; Bryce, M.R.; Levillain, E.; Viruela, R.; Orti, E.

Abstract

The first π-extended tetrathiafulvalene (exTTF) dimer in which the two exTTF units are covalently connected by 1,3-dithiole rings has been obtained in a multistep synthetic procedure involving the Ullmann cross-coupling reaction by using copper(i) thiophene-2-carboxylate (CuTC). The electronic spectrum reveals a significant electronic interaction between the exTTF units. The electrochemical study carried out by cyclic voltammetry in solution and in thin-layer conditions, and the electrochemical simulation and spectroelectrochemical (SEC) measurements confirm the electronic communication and show that the oxidation of dimer 14 occurs as two consecutive 2 e− processes D0–D0[RIGHTWARDS ARROW]D2+–D0[RIGHTWARDS ARROW]D2+–D2+. Theoretical calculations, performed at the B3P86/6-31G* level, confirm the experimental findings and predict that 142+ exists as a delocalized D.+–D.+ species in the gas phase and as a localized D2+–D0 species in solution (CH3CN or CH2Cl2). Oxidation of 142+ forms the tetracation 144+ which is constituted by two aromatic anthracene units bearing four aromatic, almost orthogonal 1,3-dithiolium cations.

Citation

Diaz, M., Illescas, B., Martin, N., Perepichka, I., Bryce, M., Levillain, E., …Orti, E. (2006). Electronic interactions in a new pi-extended tetrathiafulvalene dimer. Chemistry - A European Journal, 12(10), 2709-2721. https://doi.org/10.1002/chem.200501001

• Journal Article Type: Article
• Publication Date: 2006-03
• Journal: Chemistry - A European Journal
• Print ISSN: 0947-6539
• Publisher: Wiley
• Peer Reviewed: Peer Reviewed
• Volume: 12
• Issue: 10
• Pages: 2709-2721
• DOI: https://doi.org/10.1002/chem.200501001
• Keywords: Cyclic voltammetry, Density functional calculations, Electron donors, Spectroelectrochemistry, Tetrathiafulvalenes.