Singlet Fission in Dideuterated Tetracene and Pentacene

The impact of molecular vibrations on singlet fission, which is the spontaneous fission of a singlet exciton into two triplet excitons, is studied using ultrafast optical spectroscopy for the prototypical singlet fission chromophores tetracene and pentacene. We modify the frequency of intramolecular vibrations by deuteration, without impacting thin film structure and molecular arrangement, and study the resulting changes in exo- and endothermic singlet fission rates by comparing the deuterated and parent chromophores. We find that changes in the frequency of the C−C deformation modes of Δω=6 cm−1 and the occurrence of C−D vibrational modes do not lead to significant modifications in the singlet fission time constants. We conclude that the changes in the frequency of phonon modes induced by deuteration are too small to significantly impact the electron–phonon coupling that drives the singlet fission process.