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.
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).
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|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:||20 Nov 2014 16:37|
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