Molecular Vibration Accelerates Charge Transfer Emission in a Highly Twisted Blue Thermally Activated Delayed Fluorescence Material

In the development of new organic light-emitting diodes, thermally activated delayed fluorescence (TADF) materials have drawn interest because of their ability to upconvert electrically generated triplet excitons into singlets. Efficient TADF requires a well-balanced large transition dipole moment (μ) between the lowest excited singlet state (S1) and the ground state (S0) and a small energy splitting (ΔEST) between S1 and the lowest triplet state (T1). However, a number of highly twisted donor-acceptor-type TADF molecules have been reported to exhibit high performance in OLEDs, although these molecules may sacrifice μ in exchange for a very small ΔEST. Here, we theoretically investigate the origin of efficient emission from a perpendicularly twisted blue emitter, MA-TA. In this system, the μ value almost vanishes in the static approximation; however, vibrational contributions increase μ considerably. Hence, we show that the dynamics of excitons have a critical role in such TADF systems.