First direct in situ EPR spectroelectrochemical evidence of the superoxide anion radical.

For the first time, the superoxide anion radical was formed by electrochemical reduction of oxygen and detected in situ by EPR spectroscopy without changing the temperature. The spin susceptibilities of solid superoxide solutions were measured between 280 and 4 K showing Curie behavior. The EPR results were explained in the frame of an ion association and support the formation of a loose ion pair between the superoxide anion radical and the potassium crown ether complex. An alternative explanation for the large EPR line width of the superoxide anion radical at higher temperatures is given.