Exciplex-forming hosts with thermally activated delayed fluorescence (TADF) provide a viable opportunity to unlock the full potential of the yet-to-be improved power efficiencies (PEs) and stabilities of all-fluorescent white organic light-emitting diodes (WOLEDs), but this, however, is hindered by the lack of stable blue exciplexes. Here, an advanced exciplex system is proposed by incorporating bipolar charge-transport π-spacers into both the electron-donor (D) and the electron-accepter (A) to increase their distance for hypsochromic-shifted emission while maintaining the superior transporting ability. By using spirofluorene as the π-spacer, 3,3'-bicarbazole as the D-unit, and 2,4,6-triphenyl-1,3,5-triazine as the A-unit, a π-D and π-A exciplex with sky-blue emission and fast reverse intersystem crossing process is thereof constructed. Combining this exciplex-forming host, a blue TADF-sensitizer, and a yellow conventional fluorescent dopant in a single-emissive-layer, the fabricated warm-white-emissive device simultaneously exhibits a low driving voltage of 3.08 V, an external quantum efficiency of 21.4%, and a remarkable T80 (time to 80% of the initial luminance) of >8200 h at 1000 cd m-2 , accompanied by a new benchmark PE of 69.6 lm W-1 among all-fluorescent WOLEDs.
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