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Commercial compounds 1 (Aldrich), 3 (BDH), and 3,5-dinitrobenzoic acid
(Fluka) were recrystallized before use. The remaining compounds were
prepared and purified as published before.[25] The anions 5 and 6 were
prepared by adding alcoholic KOH to a solution of the parent neutral
compounds in ethanol until no further precipitation occurred. The
potassium salts were filtered, washed with ethanol, and dried under vacuum.
The radical anions (or radical dianions in the case of 5 and 6) were
prepared in vacuum-sealed glass cells equipped with an EPR tube and
a quartz optical cell. Reduction was achieved by contact with 0.2% Na-Hg
amalgam. The nitro compound, an excess of commercial cryptand[2.2.2]
to sequester the cation, and the Na-Hg amalgam were introduced in
different chambers of the cell under nitrogen.
The rate constants for the IET reaction were obtained by simulating
the experimental EPR spectra. The simulation program solves the Bloch
equations for a two-state model. Asymmetric line broadening was
included in the simulations by making the intrinsic line width Γ of each
ꢀ
line dependent on its nitrogen quantum number m, according to the
ꢀ
ꢀ
ꢀ 2 [42]
empirical equation Γ(m) = A + Bm+Cm .
Theoretical calculations were done using Gaussian 03.[43]
Acknowledgements
Support by Fundação Para a Ciência e Tecnologia through its
Centro de Química Estrutural and Projects PEst-OE/QUI/UI0100/
2011 and PTDC/QUI-QUI/101433/2008 is gratefully acknowledged.
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