A (π-extended tetrathiafulvalene)-fluorene conjugate. Unusual electrochemistry and charge transfer properties: The first observation of a covalent D2+-σ-A.- Redox state

Dmitrii F. Perepichka, Martin R. Bryce, Igor F. Perepichka, Svetlana B. Lyubchik, Christian A. Christensen, Nicolas Godbert, Andrei S. Batsanov, Eric Levillain, Eric J.L. McInnes, Jing P. Zhao

Resultado de pesquisarevisão de pares

63 Citações (Scopus)

Resumo

The synthesis of novel electrochemically amphoteric TTFAQ-σ-A compounds (TTFAQ = 9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene, σ = saturated spacer, A = polynitrofluorene acceptor) is reported. Their solution redox behavior is characterized by three single-electron reduction and one two-electron oxidation waves. Electrochemical quasireversibility of the TTFAQ2+ state and a low Eox - Erec gap (≈0.25 V) for 3-(9-dicyanomethylene-4,5,7-trinitrofluorene-2-sulfonyl)-propionic acid 2-[10-(4,5-dimethyl-[1,3]dithiol-2-ylidene)-9, 10-dihydroanthracen-9-ylidene]-5-methyl-[1,3]dithiol-4-ylmethyl ester (10) has enabled the electrochemical generation of the hitherto unknown transient D2+-≠-A.- state as observed in cyclic voltammetry and time-resolved spectroelectrochemistry. The ground state of compound 10 was shown to be ionic in the solid but is essentially neutral in solution (according to electron paramagnetic resonance). The X-ray structure of an intermolecular 1:2 complex between 2-[2,7-bis(2-hydroxyethoxy)-9,10-bis(4,5-dimethyl-[1,3] dithiol-2-ylidene)-9,10-dihydroanthracene and 2,5,7-trinitro-4-bromo-9-dicyanomethylenefluorene, 14·(17)2, reveals, for the first time, full electron transfer in a fluorene charge-transfer complex.

Idioma originalInglês
Páginas (de-até)14227-14238
Número de páginas12
RevistaJournal of the American Chemical Society
Volume124
Número de emissão47
DOIs
Estado da publicaçãoPublicadas - 27 nov. 2002
Publicado externamenteSim

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