Solvation effects on the electron-transfer reaction of TCNQ anion radical and 2,3-dichloro-5,6-dicyano-p-benzoquinone.
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Rate constants were obtained with a temperature-jump apparatus for the electron-transfer reaction between 7,7,8,8-tetracyanoquinodimethane anion radical and 2,3-dichloro-5,6-dicyano-<I>p</I>-benzoquinone in acetonitrile/ tetrahydrofuran (MeCN/THF) and in acetonitrile/water (MeCN/H<SUB>2</SUB>O) mixtures. In MeCN/THF, the forward rate constant (<I>k</I>) was determined in three kinds of mixed solvents: <I>k</I>=(5±2)×10<SUP>9</SUP> M<SUP>−1</SUP>s<SUP>−1</SUP> (pure MeCN), (2.2±0.2)×10<SUP>9</SUP> M<SUP>−1</SUP>s<SUP>−1</SUP> (1: 2 MeCN/THF), and (6±2)×10<SUP>8</SUP> M<SUP>−1</SUP>s<SUP>−1</SUP> (1: 10 MeCN/THF) at 25±2°C. In MeCN/H<SUB>2</SUB>O the forward rate constant increases with the square of the H<SUB>2</SUB>O concentration in the range of [H<SUB>2</SUB>O]=2–10 M; <I>k</I>=<I>k</I><SUB>0</SUB>[H<SUB>2</SUB>O]<SUP>2</SUP> with k<SUB>0</SUB>=(1.0±0.2)×10<SUP>6</SUP> M<SUP>−3</SUP>s<SUP>−1</SUP> at 25±2 °C. The results are discussed in terms of the specific solvation and the ion-pairing of ion radicals.
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