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Engineering a remarkably low HOMO-LUMO gap by covalent linkage of a strong pi-donor and a pi-acceptor-tetrathiafulvaleneu-sigma-polynitrofluorene diads : their amphoteric redox behavior, electron transfer and spectroscopic properties.

Perepichka, D. F. and Bryce, M. R. and Batsanov, A. S. and McInnes, E. J. L. and Zhao, J. P. and Farley, R. D. (2002) 'Engineering a remarkably low HOMO-LUMO gap by covalent linkage of a strong pi-donor and a pi-acceptor-tetrathiafulvaleneu-sigma-polynitrofluorene diads : their amphoteric redox behavior, electron transfer and spectroscopic properties.', Chemistry : a European journal., 8 (20). pp. 4656-4669.

Abstract

Novel R3TTF-sigma-A compounds 14, 16 and 19 (R3TTF = trial-kyltetrathiafulvalene, sigma = saturated spacer, A = polynitrofluoren-9-dicyano-methylene acceptor) incorporating very strong donor and acceptor moieties have been synthesized by condensation of the corresponding R3TTF-sigma-fluoren-9-one diads with malononitrile. Reversible five-step amphoteric redox behavior has been observed with an extremely low HOMO-LUMO gap (approximate to 0.3 eV). For compound 14 a strong EPR signal is observed in the solid state, ascribed to intermolecular complexation: a less intense signal is seen in solution, corresponding to ca. 2% of the molecules existing in a radical form at room temperature. Intramolecular charge transfer in diads 14 and 16 is manifested in strong absorption bands in the near-IR region of their electronic spectra. Spectroelectrochemical data reveal marked electrochromic behavior in the visible and near-IR region of both compounds. The first X-ray crystal structure of a fluorene radical-anion salt is reported, namely the copper salt of 2,4,5,7-tetranitro-9-dicyanomethylenefluorene (1:1 stoichiometry).

Item Type:Article
Full text:Full text not available from this repository.
Publisher Web site:http://dx.doi.org/10.1002/1521-3765(20021018)8:20<4656::AID-CHEM4656>3.0.CO;2-1
Record Created:26 Apr 2007
Last Modified:08 Apr 2009 16:30

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