Triplet exciton dynamics of pure organics with halogen substitution boosted two photon absorption and room temperature phosphorescence: A theoretical perspective

Organic room temperature phosphorescence (RTP) molecules have shown promising applications in organic light emitting diodes and vivo imaging. Thus, triplet exciton dynamics in solid phase should be revealed and the molecule should possess large two photon absorption (TPA) cross sections under near-infrared excitation. The effects of halogen substitution and intermolecular interaction on RTP and TPA properties are studied at molecular level for a series of derivatives. Surrounding environment in solid phase is considered by combined quantum mechanics and molecular mechanics method. Intermolecular interactions are evaluated by the independent gradient model and calculated through the molecular force field energy decomposition method. Minimum energy crossing point, Huang-Rhys factor and reorganization energy are discussed, triplet exciton dynamics are investigated by thermal vibration correlation function method. Results indicate that the largest TPA cross sections are found for molecule in water. The halogen substitution can enlarge the proportion of (π, π*) and facilitate the intersystem crossing process. Restricted intramolecular rotation motions of dihedral angle in low frequency regions are found for Br-Np-Cz-BF2 in solid phase. While enhanced vibrations of bond length and bond angle in high frequency regions are detected for I-Np-Cz-BF2. Effects of halogen substitution and intermolecular interaction on triplet exciton dynamics are highlighted.