The study of intramolecular decay and intermolecular energy transfer for phosphorescent organic light-emitting devices.

Due to the huge potential of organic light-emitting diodes (OLEDs) in optical display devices, the exciton utilization of devices should be elucidated comprehensively to achieve a high external quantum efficiency (EQE). In this study, theoretical calculations of intramolecular excited state decay and intermolecular excitation energy transfer (EET) were conducted to investigate the differences in EQE between the two studied systems. Compared to the PtOO7-based system (using PtOO7 as the guest and 26mCPy as the host), the greater EQE of the PtON7-based system (using PtON7 as the guest and 26mCPy as the host) was mainly governed by the stronger energy transfer efficiency, with a secondary role being played by the higher photoluminescence quantum yield of the emitter. We confirmed that the different triplet EET (TEET) rates mainly contribute to the difference in the energy transfer efficiency between two studied systems, where the higher TEET rate from 26mCPy to PtON7 can be attributed to the restrained structural deformation of PtON7 and the desirable energy gap in the energy transfer process. Our calculations indicated that the electronic structure can evidently affect the intramolecular excited state decay and intermolecular excitation energy transfer. In addition, considering the environmental effects on the emission spectra of the emitters, the simulated spectra were consistent with the experimental measurements, which indicated that our descriptions of electronic structures are accurate; furthermore, an effective description of the molecular environment should be obtained. Our computational protocol successfully explored the relationship between the electronic structures, intramolecular excited state decay, and intermolecular excitation energy transfer, which can provide a deep understanding for the design and development of high-quality OLEDs from a molecular perspective.