Crucial Role of Defect States in the Ultralong Phosphorescence of Organic Molecular Crystals.

Ultralong organic phosphorescence (UOP) in pure organic molecular crystals has attracted a lot of interest recently. There is much debate on the emission mechanism of this UOP. Two recent experimental works published in Nat. Photonics 2019, 13, 406-411 and Nat. Mater. 2021, 20, 175-180 attribute UOP in the 2,4,6-trimethoxy-1,3,5-triazine (TMOT) crystals and the carbazole crystals to H-aggregation of the TMOT molecules or the formation of charge-transfer excitons between the carbazole and impurity molecules. Our first-principles many-body Green's function theory calculations show that the lowest triplet states of these two crystals are in fact the localized defect states originating from the twisted TMOT molecules and the impurities, respectively. Energies of the H-aggregation-induced exciton and the charge-transfer exciton are too high to account for UOP. UOP should be mainly due to the little orbital overlap between the localized defect state and the delocalized band edges of the crystal. Strong intermolecular interactions suppress nonradiative decay of the triplet exciton localized on the defect.