One-Way Geometrical Isomerization of 1,1-Diarylethenes Induced by Photosensitized Electron Transfer

Abstract

One-way geometrical isomerization around a C=C bond of 1,1-diary1-2-t-butylethene is achieved upon photoirradiation of cyanoaromatics as a light-absorbing sensitizer. In the thermochemical view, there is no difference between both E and Z isomers of the ethene. Key intermediate is a putative distonic radical cation which is a unique one having a spatially separate radical and ionic centers on the molecular framework. Generation of such an intermediate is due to the presence of a π-donating substituent on an aromatic ring and a bulky t-butyl group. Molecular oxygen interacts as superoxide with the C=C bond of the radical cation in a [supra + antara] manner to give a decomposition product, i.e. a benzophenone derivative and pivalaldehyde, via a dioxetane and competitively, one geometrical isomer of the ethene is afforded by splitting oxygen before making two bonds with the ethene radical cation and superoxide.