Temperature-Dependent Photochemistry of 1,3-Diphenylpropenes. The Di-π-Methane Reaction Revisited

The temperature-dependent photochemical behavior of 1,3-diphenylpropene and several of its 3-substituted derivatives has been investigated over a wide temperature range. The singlet state is found to decay via two unactivated processes, fluorescence and intersystem crossing, and two activated processes, trans,cis isomerization and phenyl-vinyl bridging. The latter activated process yields a diradical intermediate which partitions between ground-state reactant and formation of the di-π-methane rearrangement product. Kinetic modeling of temperature-dependent singlet decay times and quantum yields of fluorescence, isomerization, di-π-methane rearrangement, and nonradiative decay provides rate constants and activation parameters for each of the primary and secondary processes. Substituents at the 3-position are found to have little effect on the electronic spectra or unactivated fluorescence and intersystem crossing pathways. However, they do effect the activated primary and secondary processes. Thus, the product ratios are highly temperature dependent.