Mechanistic Studies of Adamantylacetophenones with Competing Reaction Pathways in Solution and in the Crystalline Solid State

Photochemical reactions in crystals occur under conditions of highly restricted molecular mobility such that only one product is generally obtained, even when there are many others that can be observed in the gas phase or in solution. A series of 2-(1-adamantyl)-o-alkyl-acetophenones with γ-hydrogen atoms on both the adamantyl and ortho aromatic groups was selected to determine whether one can engineer and observe competing Norrish type II reaction pathways in the crystalline state. It was shown that excited state competition for hydrogen abstraction between secondary adamantyl and benzylic hydrogens is affected not only by the relative bond dissociation energies but also by the molecular conformation in the crystal. The subsequent fate of the resulting biradical species is determined by competition between radical recombination to form the photoproduct and reverse hydrogen atom transfer to regenerate the starting ketone. Crystallographic information, photoproduct distributions in solution and in the solid state, and the results of multiple mechanistic experiments, including transient absorption spectroscopy in acetonitrile and with nanocrystals suspended in water, are reported. The results demonstrate that it is possible to engineer competing reactions in crystals and that consideration of all of the aforementioned factors is necessary to account for the observed photoproduct selectivity.