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Díaz MC, Illescas BM, Martín N, et al. Highly conjugated p-quinonoid pi-extended tetrathiafulvalene derivatives: a class of highly distorted electron donors. Chemistry. 2004;10(8):2067-77doi: 10.1002/chem.200305555.
Díaz, M. C., Illescas, B. M., Martín, N., Viruela, R., Viruela, P. M., Ortí, E., Brede, O., Zilbermann, I., & Guldi, D. M. (2004). Highly conjugated p-quinonoid pi-extended tetrathiafulvalene derivatives: a class of highly distorted electron donors. Chemistry (Weinheim an der Bergstrasse, Germany), 10(8), 2067-77. https://doi.org/10.1002/chem.200305555
Díaz, Marta C, et al. "Highly conjugated p-quinonoid pi-extended tetrathiafulvalene derivatives: a class of highly distorted electron donors." Chemistry (Weinheim an der Bergstrasse, Germany) vol. 10,8 (2004): 2067-77. doi: https://doi.org/10.1002/chem.200305555
Díaz MC, Illescas BM, Martín N, Viruela R, Viruela PM, Ortí E, Brede O, Zilbermann I, Guldi DM. Highly conjugated p-quinonoid pi-extended tetrathiafulvalene derivatives: a class of highly distorted electron donors. Chemistry. 2004 Apr 19;10(8):2067-77. doi: 10.1002/chem.200305555. PMID: 15079847.
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Chemistry. 2004 Apr 19;10(8):2067-77. doi: 10.1002/chem.200305555.

Highly conjugated p-quinonoid pi-extended tetrathiafulvalene derivatives: a class of highly distorted electron donors.

Chemistry (Weinheim an der Bergstrasse, Germany)

Marta C Díaz, Beatriz M Illescas, Nazario Martín, Rafael Viruela, Pedro M Viruela, Enrique Ortí, Ortwin Brede, Israel Zilbermann, Dirk M Guldi

Affiliations

  1. Departamento Química Orgánica, Facultad de Ciencias Químicas, Universidad Complutense, 28040 Madrid, Spain.

PMID: 15079847 DOI: 10.1002/chem.200305555

Abstract

A new class of pi-extended TTF-type electron donors (11 a-c) has been synthesized by Wittig-Horner olefination of bianthrone (9) with 1,3-dithiole phosphonate esters (10 a-c). In cyclic voltammetry experiments, donors 11 a-c reveal a single, electrochemically irreversible oxidation-yielding the corresponding dicationic products-at relatively low oxidation potentials (approximately 0.7-0.8 V). Theoretical calculations, performed at the DFT level (B3 P86/6-31 G*), predict a highly-folded C(2h) structure for 11 a. In the ground state, the molecule adopts a double saddle-like conformation to compensate the steric hindrance. The calculations suggest that the intramolecular charge transfer associated with the HOMO-->LUMO transition is responsible for an absorption band observed above 400 nm. While the radical cation 11 a*+ retains the folded C(2h) structure predicted for the neutral molecule as the most stable conformation, the dication 11 a(2+) has a fully aromatic D(2) structure, formed by an orthogonal 9,9'-bianthryl central unit to which two singly-charged dithiole rings are attached. The drastic conformational changes that compounds 11 undergo upon oxidation account for their electrochemical properties. By means of pulse radiolysis measurements, radical-induced one-electron oxidation of 11 a-c was shown to lead to the radical cation species (11 a-c*+), which were found to disproportionate with generation of the respective dication species (11 a-c(2+)) and the neutral molecules (11 a-c).

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