Electron Spin Resonance of Irradiated Single Crystals of Sodium and Potassium 1-Oximinopropionates

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Abstract
ESR studies have been made with single crystals of sodium 1-oximinopropionate irradiated at −196°C and at room temperature. The principal values and axes of the g and hyperfine tensors of the trapped radicals have been determined. The analysis of the observed data has indicated that the σ-electron radicals CH3C(COO−)=NO are trapped at −196°C and at room temperature. It has been found that the electronic structures of the trapped radicals at these two temperatures are essentially the same, but that the environments of the radicals are very different from each other. After the crystal had been heated at 50°C for a week, the σ-electron radical vanished and the π-electron radicals, CH3C(OH)(COO−)NHO· and CH3CR’-(COO−)NRO·, appeared. The former may be formed in the solid state by adding a crystal water molecule to the unsaturated radical. The trapped radicals in irradiated single crystals of potassium 1-oximinopropionate were also studied at room temperature and after having been heated at 50°C. They are the σ-electron radical and the π-electron radical respectively, with structures similar to those of the sodium salt. The radical pairs have been observed in irradiated single crystals of the sodium salt at −196°C.

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