DECOMPOSITION OF DIOXETANE INDUCED BY ELECTRON-TRANSFER FROM A PHOTOEXCITED LANTHANIDE ION

The photodecomposition of adamantylideneadamantane-1,2-dioxetane (1) i n the presence of Ce3+ is discovered. Electron transfer plays a domina nt role in the reaction mechanism. The photoirradiation of solutions o f 1 and CeCl3 within the absorption region of the latter leads to the decomposition of 1 with the initial quantum yield PHI = 0.29 +/- 0.03. The reaction is caused by the dynamic extinction of the photoluminesc ence of Ce3+ ions by dioxetane 1. Adamantanone is the main product of the photocatalytic reaction. However, side products of the interactio n of the intermediate 1,4-dioxyradical anion with the solvent are also formed.