Origin of Intense Luminescence from Supramolecular 2D Molecular Crystals

Abstract Luminescence enhancement in 2D molecular crystals (2D crystals) is promising for a variety of optical applications, yet the availability is limited because of unclear mechanism and inefficient design strategy of luminescence control. Herein, the room temperature phosphorescence from micron long molecular thin free‐standing 2D crystals of a mono‐cyclometalated Ir(III) complex designed at the water surface is reported. A large luminescence enhancement is observed from the 2D crystals at 300 K, which is comparable with the rigidified solution at 77 K suggesting room temperature phosphorescence origin of the luminescence. In situ synchrotron grazing incidence X‐ray diffraction measurements determine the constituent centered rectangular unit cells with precise molecular conformation that promotes the formation of 2D crystals. The molecular crystal design leads to a reduced singlet‐triplet energy gap (ΔE_ST) and mixing of singlet‐triplet states by spin‐orbit coupling (SOC) for efficient intersystem crossing, which explains the phosphorescence origin at room temperature and luminescence enhancement. The supramolecular assembly process provides an elegant design strategy to realize room temperature phosphorescence from 2D crystals by rigid intermolecular interactions.