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A (pi-extended tetrathiafulvalene)-fluorene conjugate : unusual electrochemistry and charge transfer properties : the first observation of a covalent D2+-sigma-A(center dot-) redox state.

Perepichka, D. F. and Bryce, M. R. and Perepichka, I. F. and Lyubchik, S. B. and Christensen, C. A. and Godbert, N. and Batsanov, A. S. and Levillain, E. and McInnes, E. J. L. and Zhao, J. P. (2002) 'A (pi-extended tetrathiafulvalene)-fluorene conjugate : unusual electrochemistry and charge transfer properties : the first observation of a covalent D2+-sigma-A(center dot-) redox state.', Journal of the American Chemical Society., 124 (47). pp. 14227-14238.

Abstract

The synthesis of novel electrochemically amphoteric TTFAQ-sigma-A compounds (TTFAQ = 9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene, sigma = 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 quasi reversibility of the TTFAQ(2+) state and a low E-ox - E-red gap (approximate to0.25 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-ylid enel]-5-methyl-[1,3]dithiol-4-ylmethyI ester (10) has enabled the electrochemical generation of the hitherto unknown transient D2+-sigma-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(4,5dimethyl-[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.

Item Type:Article
Full text:Full text not available from this repository.
Publisher Web site:http://dx.doi.org/10.1021/ja012518o
Record Created:15 May 2007
Last Modified:08 Apr 2009 16:31

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