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Electronic interactions in a new pi-extended tetrathiafulvalene dimer.
- Source :
-
Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2006 Mar 20; Vol. 12 (10), pp. 2709-21. - Publication Year :
- 2006
-
Abstract
- The first pi-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.
Details
- Language :
- English
- ISSN :
- 0947-6539
- Volume :
- 12
- Issue :
- 10
- Database :
- MEDLINE
- Journal :
- Chemistry (Weinheim an der Bergstrasse, Germany)
- Publication Type :
- Academic Journal
- Accession number :
- 16429472
- Full Text :
- https://doi.org/10.1002/chem.200501001