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Electronic Interactions in a New π‐Extended Tetrathiafulvalene Dimer
Author(s) -
Díaz Marta C.,
Illescas Beatriz M.,
Martín Nazario,
Perepichka Igor F.,
Bryce Martin R.,
Levillain Eric,
Viruela Rafael,
Ortí Enrique
Publication year - 2006
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.200501001
Subject(s) - tetrathiafulvalene , dimer , delocalized electron , chemistry , electrochemistry , anthracene , cyclic voltammetry , covalent bond , photochemistry , computational chemistry , molecule , electrode , organic chemistry
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 D 0 –D 0 →D 2+ –D 0 →D 2+ –D 2+ . Theoretical calculations, performed at the B3P86/6‐31G* level, confirm the experimental findings and predict that 14 2+ exists as a delocalized D .+ –D .+ species in the gas phase and as a localized D 2+ –D 0 species in solution (CH 3 CN or CH 2 Cl 2 ). Oxidation of 14 2+ forms the tetracation 14 4+ which is constituted by two aromatic anthracene units bearing four aromatic, almost orthogonal 1,3‐dithiolium cations.