Acceptor-Donor-Acceptor π -Stacking Boosts Intramolecular Through-Space Charge Transfer towards Efficient Red TADF and High-Performance OLEDs.

Organic push-pull systems featuring through-space charge transfer (TSCT) excited states have been disclosed to be capable of exhibiting thermally activated delayed fluorescence (TADF), but to realize high-efficiency long-wavelength emission still remains a challenge. Herein, we report a series of strongly emissive orange-red and red TSCT-TADF emitters having (quasi)planar and rigid donor and acceptor segments which are placed in close proximity and orientated in a cofacial manner. Emission maxima ( λ em ) of 594-599 nm with photoluminescence quantum yields (PLQYs) of up to 91% and delayed fluorescence lifetimes of down to 4.9  μ s have been achieved for new acceptor-donor-acceptor (A-D-A) molecules in doped thin films. The presence of multiple acceptors and the strong intramolecular π -stacking interactions have been unveiled to be crucial for the efficient low-energy TSCT-TADF emissions. Organic light-emitting diodes (OLEDs) based on the new A-D-A emitters demonstrated electroluminescence with maximum external quantum efficiencies (EQEs) of up to 23.2% for the red TSCT-TADF emitters. An EQE of 18.9% at the brightness of 1000 cd m -2 represents one of the highest values for red TADF OLEDs. This work demonstrates a modular approach for developing high-performance red TADF emitters through engineering through-space interactions, and it may also provide implications to the design of TADF emitter with other colours.