Inducing Singlet Fission in Perylene Thin Films by Molecular Contortion

Singlet fission occurs only in a limited number of molecules, and expanding the molecular toolbox is necessary for progress. Here, we apply the molecular contortion strategy to tune singlet and triplet energies and observe changes in the excited-state dynamics that are consistent with singlet fission playing a role in thin films of contorted perylene. Perylene is a prototypical molecular chromophore, which does not undergo singlet fission in its planar form from its S₁ state. The tuning of the energetics that control singlet fission through molecular contortion can be applied to a large repertoire of established molecular chromophores.