Exploration of Quenching Pathways of Multiluminescent Acenes Using the GRRM Method with the SF-TDDFT Method

The quenching pathways were investigated for three types of multiluminescent acene derivatives, which show environment-dependent fluorescence. Spin-flip time dependent density functional theory (SF-TDDFT) combined with the Global Reaction Route mapping (GRRM) strategy is employed to locate minimum-energy conical intersections (MECIs). The energies and geometries of the MECIs relative to the Franck-Condon (FC) state control the difference in fluorescence behavior among the three derivatives. For the molecule with a phenyamide moiety, a MECI with energy lower than the FC state with large geometrical change from V-type to flat structure provides an efficient internal conversion (quenching) pathway in solution. For the same molecule, in a solid, this large geometrical change is inhibited, and the second MECI, with an energy lower than FC but higher than the first MECI requiring only a small geometry change of CH out-of-plane bending, contributes to the quenching. The molecule with the napthaleneimide moiety has only one low-energy MECI that requires large geometrical change from the V-type to flat structure. Although this MECI provides the quenching pathway in solution, in the solid, this large motion is inhibited, and the molecule will stay in the excited state and emit. The molecule with an anthraceneimide moiety has no conical intersection lower than the FC state, and no quenching pathway is available in solution or solid. In addition, in this molecule, at the local minimum of the excited state, the dipole transition to the ground state is allowed, and this molecule prefers emission rather than internal conversion.