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

Abstract

A new iptycene unequivocally validates homoconjugation as a viable strategy to simultaneously enhance TADF reverse intersystem crossing and radiative decay. 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 (Δ E ST ) in a single luminophore. We present a TADF-active iptycene that clearly demonstrates that homoconjugation can be harnessed as a viable design strategy towards answering this challenge. A homoconjugated analogue of an established quinoxaline-based TADF luminophore has been produced by fusing three of these luminophores together across a shared triptycene 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 ( k Sr), delayed fluorescence lifetime ( τ TADF ), and rate of reverse intersystem crossing ( k rISC ), all while narrowing the Δ E 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.