Reaction selectivity in solid state photochemistry

摘要: Abstract Steric compression, arising from intermolecular or H...H non-bonded repulsive interactions generated along the reaction pathway, is used to explain abnomal solid state photoreactivity. Computer simulations of motions involved in each case, with calculations resulting steric compression energies were performed. Three systems studied: ( A ) Enone photorearrangements, where observed changes photoreactivity eight closely related α,β-unsaturated cyclohexenones are correlated their crystal and molecular structures as determined by X-ray diffraction methods. B Failure [2+2] photocycloadditilon an ketone when irradiated despite almost perfect lattice alignment potentially reactive double bonds. C An unsymmetrically substituted ene-dione for which solution photoreactlon results four products photoreaction yields only one.