Role of Conical Intersections on the Efficiency of Fluorescent Organic Molecular Crystals

Organic molecular crystals are attractive materials for luminescent applications because of their promised tunability. However, the link between the chemical structure and emissive behavior is poorly understood because of the numerous interconnected factors which are at play in determining radiative and nonradiative behaviors at the solid-state level. In particular, the decay through conical intersection dominates the nonadiabatic regions of the potential energy surface, and thus, their accessibility is a telling indicator of the luminosity of the material. In this study, we investigate the radiative mechanism for five organic molecular crystals which display a solid-state emission, with a focus on the role of conical intersections in their photomechanisms. The objective is to situate the importance of the accessibility of conical intersections with regards to emissive behavior, taking into account other nonradiative decay channels, namely, vibrational decay, and exciton hopping. We begin by giving a brief overview of the structural patterns of the five systems within a larger pool of 13 crystals for a richer comparison. We observe that because of the prevalence of sheet like and herringbone packing in organic molecular crystals, the conformational diversity of crystal dimers is limited. Additionally, similarly spaced dimers have exciton coupling values of a similar order within a 50 meV interval. Next, we focus on three exemplary cases, where we disentangle the role of nonradiative decay mechanisms and show how rotational minimum energy conical intersections in vacuum lead to puckered ones in the crystal, increasing their instability upon crystallization in typical packing motifs. In contrast, molecules with puckered conical intersections in vacuum tend to conserve this trait upon crystallization, and therefore, their quantum yield of fluorescence is determined predominantly by other nonradiative decay mechanisms.