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The rate of a homogeneous electron transfer reaction between a neutral molecule and its radical anion has been measured for a number of aromatic hydrocarbons.1-5 The rate of electron exchange between different aromatic hydrocarbons (heterogeneous electron transfer) has not previously been measured by e.s.r. techniques. Arai et al.6 have measured rate constants k for heterogeneous electron transfer reactions in isopropanol by pulse radiolysis studies. Analysis of their experimental results depends on the equilibrium position being favoured very much in one direction. For those molecules with similar electron affinities, it is possible to measure the rate of heterogeneous electron transfer by e.s.r. line broadening. We have estimated the rate constant for heterogeneous electron transfer between anthracene anions and pyrene molecules by this method. An approximately 1 0 3 ~ solution of anthracene dianions was prepared in 1,2dimethoxyethane (DME) by potassium reduction.7 Neutral anthracene (A) or pyrene (P) was added to convert the dianions into monoanions. Weighed quantities of neutral pyrene were then added through breakseals. The following reactions occurred.

Electron exchange between anthracene anions and pyrene molecules in solution