Face‐to‐Face Orientation of Quasiplanar Donor and Acceptor Enables Highly Efficient Intramolecular Exciplex Fluorescence

Abstract Intramolecular through‐space charge‐transfer (TSCT) excited states have been exploited for developing thermally activated delayed fluorescence (TADF) emitters, but the tuning of excited state dynamics by conformational engineering remains sparse. Designed here is a series of TSCT emitters with precisely controlled alignment of the donor and acceptor segments. With increasing intramolecular π–π interactions, the radiative decay rate of the lowest singlet excited state (S 1 ) progressively increased together with a suppression of nonradiative decay, leading to significantly enhanced photoluminescence quantum yields of up to 0.99 in doped thin films. A high‐efficiency electroluminescence device, with a maximum external quantum efficiency (EQE) of 23.96 %, was achieved and maintains >20 % at a brightness of 1000 cd m −2 . This work sheds light on the importance of conformation control for achieving high‐efficiency intramolecular exciplex emitters.