Simultaneous enhancement of thermally activated delayed fluorescence and photoluminescence quantum yield via homoconjugation

A critical challenge facing thermally activated delayed fluorescence (TADF) is to facilitate rapid and efficient electronic transitions while ensuring a narrow singlet-triplet energy gap (ΔE_ST) in a single luminophore. We present a TADF-active iptycene that clearly demonstrates that homoconjugation can be harnessed as a viable design strategy toward answering this challenge. A homoconjugated analogue of an established quinoxaline-based TADF luminophore has been produced by trimerization through an iptycene core. Homoconjugation was confirmed by electrochemistry, and as a direct consequence of this phenomenon we observed synergistic improvements to photoluminescence quantum yield (Φ_PL), radiative rate of singlet decay (krS), delayed fluorescence lifetime (τ_TADF), and rate of reverse intersystem crossing (krISC), all while narrowing the ΔE_ST. The enhancement is rationalised with TD-DFT calculations including spin-orbit coupling (SOC). A facile synthesis, the ubiquity of the pyrazine motif in state-of-the-art TADF materials of all colours, and the extent of the overall performance enhancement leads to a great potential for generality.