Polymorphism Dependent 9-Phosphoanthracene Derivative Exhibiting Thermally Activated Delayed Fluorescence: A Computational Investigation
Arun K. Pal, Kalishankar Bhattacharyya, Ayan Datta
Abstract
Polymorphs of anthracene derivatives exhibit diverse photophysical properties that can help to develop efficient organic-based photovoltaic devices. 10-Anthryl-9-phosphoanthracene (10-APA) shows different photophysical behaviors for the solid state due to its variety in crystalline arrangement. Herein, we investigate the ground and excited-state properties of the monomer and two different polymorphs of 10-APA from first-principles. Calculations reveal that strong spin–orbit coupling (SOC) between first excited singlet state (S1) and triplet manifolds at their S1-optimized geometries enabling the reverse intersystem crossing (RISC). The electron–vibration coupling (Huang–Rhys factor) in the excited state is the most relevant factor here. For both ISC and RISC, a similarity in Huang–Rhys factors for the molecular vibration along the π···π stacking at low-frequency region makes the rates effective. On the other side, the nonvanishing vibronic relaxation modes provide a relatively slower RISC rate in the red crystal. However, for the red crystal, small reorganization energy (λ) and large Huang–Rhys factor toward S1 → S0 conversion reduce nonradiative decay, leading to a prompt fluorescence. As the feasibility of S1 ↔ T1 conversion increases in the yellow dimer, it allows a delay in fluorescence emission, leading to thermally activated delayed fluorescence (TADF).