Reverse intersystem
crossing (RISC), originally considered forbidden in purely organic materials,
has been recently enabled by minimizing the energy gap between the lowest
singlet excited state (S<sub>1</sub>) and lowest triplet state (T<sub>1</sub>) in
thermally activated delayed
fluorescence (TADF) systems.
However, direct spin-inversion between S<sub>1</sub> and T<sub>1</sub> is still
inefficient when both states are of the same charge transfer (CT) nature (i.e. <sup>1</sup>CT
and <sup>3</sup>CT, respectively). Intervention of locally excited triplet
states (<sup>3</sup>LE) between <sup>1</sup>CT and <sup>3</sup>CT is expected
to trigger fast spin-flip. Here, we report on the systematic-design of the
ideal TADF molecules
with near-degenerate <sup>1</sup>CT, <sup>3</sup>CT and <sup>3</sup>LE states
by controlling the through-space distance between the donor and acceptor
segments in a molecule with tilted intersegment angles. The new system realizes
very fast RISC with a rate constant (<i>k</i><sub>RISC</sub>) of 1.2×10<sup>7</sup> s<sup>−1</sup>. The large <i>k</i><sub>RISC</sub>
of the emitter resulted in great device performance in the applications to blue
TADF assisted fluorescence organic light-emitting diodes (OLEDs) as well as
TADF-emitter OLEDs.<br>