Electronic absorption spectra and geometry of molecular ions generated from stilbene and related compounds. III. Radical ions of (Z)-stilbene and its .ALPHA.,.BETA.-dialkyl derivatives.

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The radical ions of (Z)-stilbene and its α,β-dialkyl derivatives were produced by γ-ray irradiation of the parent compounds in frozen matrices at 77 K, and their geometries were investigated by electronic absorption spectroscopy. While the relaxed geometries of the radical ions of (Z)-stilbene are probably similar to that of the neutral molecule, those of the radical ions of the α,β-dialkyl derivatives are appreciably different from those of the neutral molecules: The torsion angle of the central ethylenic bond is distinctly larger and that of each C–Ph bond is probably smaller in the radical ions than in the neutral molecules. On illumination the radical ions of (Z)-stilbene isomerize to the E isomers, but those of the α,β-dialkyl derivatives do not. A mechanism of the photoisomerization is proposed, and an interpretation of the difference in the photochemical behavior between the unsubstituted stilbene radical ions and the α,β-dialkyl derivatives is given.
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