Structural Transformations in Crystals Induced by Radiation and Pressure. Part 7. Molecular and Crystal Geometries as Factors Deciding about Photochemical Reactivity under Ambient and High Pressures

摘要

We studied the photochemical reactivity of salts of 4-(2,4,6-triisopropylbenzoyl)benzoic acid with propane-1,2-diamine ( 1 ), methanamine ( 2 ), cyclohexanamine ( 3 ), and morpholine ( 4 ), for compounds ( 1 ), ( 3 ), and ( 4 ) at 0.1 MPa and for compounds ( 1 ) and ( 2 ) at 1.3 GPa and 1.0 GPa, respectively. The changes in the values of the unit cell parameters after UV irradiation and the values of the intramolecular geometrical parameters indicated the possibility of the occurrence of the Norrish–Yang reaction in the case of all the compounds. The analysis of the intramolecular geometry and free spaces revealed which o- isopropyl group takes part in the reaction. For ( 1 ), the same o -isopropyl group should be reactive at ambient and high pressures. In the case of ( 2 ), high pressure caused the phase transition from the space group I2/a with one molecule in the asymmetric unit cell to the space group P 1 ˉ with two asymmetric molecules. The analysis of voids indicated that the Norrish–Yang reaction is less probable for one of the two molecules. For the other molecule, the intramolecular geometrical parameters showed that except for the Norrish–Yang reaction, the concurrent reaction leading to the formation of a five-membered ring can also proceed. In ( 3 ), both o- isopropyl groups are able to react; however, the bigger volume of a void near 2-isopropyl may be the factor determining the reactivity. For ( 4 ), only one o- isopropyl should be reactive.