Phosphine‐Oxide‐Balanced Intra‐ and Interchain Through‐Space Charge Transfer in Thermally Activated Delayed Fluorescence Polymers: Beyond 30% External Quantum Efficiency

Through-space charge transfer (TSCT) is crucial for developing highly efficient thermally activated delayed fluorescence polymers. The balance of intra- and interchain TSCT can markedly improve performance, but it is still a big challenge. In this work, an effective strategy for "intra- and interchain TSCT balance" is demonstrated by way of a series of non-conjugated copolymers containing a 9,9-dimethylacridine donor and triazine-phosphine oxide (PO)-based acceptors. Steady-state and transient emission spectra indicate that compared to the corresponding blends, the copolymers can indeed achieve balanced intra- and interchain TSCT by accurately optimizing the inductive and steric effects of the acceptors. The DPOT acceptor with the strongest electron-withdrawing ability and the second bigger steric hindrance endows its copolymers with state-of-the-art photoluminescence and electroluminescence quantum efficiencies beyond 95% and 32%, respectively. This demonstrates that, compared to other congeners, the synergistic inductive and steric effects effectively enhance TSCT in DPOT-based copolymers for radiation, and suppress singlet and triplet quenching. The record-high efficiencies of its devices make this kind of copolymers hold the potential for low-cost, large-scale, and high-efficiency applications.