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 (S) and the ground state (S) and a small energy splitting (Δ) between S and the lowest triplet state (T). 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 Δ. 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.