Structure–Property Correlation in Luminescent Indolo[3,2-b]indole (IDID) Derivatives: Unraveling the Mechanism of High Efficiency Thermally Activated Delayed Fluorescence (TADF)

A series of indolo[3,2- b ]indole (IDID) derivatives are designed as a novel structural platform for thermally activated delayed fluorescence (TADF) emitters. Intramolecular charge transfer (ICT)-type molecules consisting of IDID donor (D) and various acceptor (A) moieties are synthesized and characterized in the protocol of the systematical structure–property correlation. IDID derivatives exhibit high efficiency, prompt fluorescence as well as TADF with emission ranges tuned by the chemical structure of the acceptor units. Interestingly, almost all of the IDID derivatives show an identical energy level of the lowest triplet excited state (T 1 ) attributed to the locally excited triplet state of the IDID backbone ( 3 LE ID ), while that of their lowest singlet excited state (S 1 ) is largely tuned by varying the acceptor units. Thus, we demonstrate the underlying mechanism in terms of the molecular engineering. Among the compounds, Tria-phIDID and BP-phIDID generate efficient delayed fluorescence based on the small energy gap between the lowest singlet and triplet excited states (Δ E ST ) and mediation of the 3 LE ID state. Organic light-emitting diodes with these Tria-phIDID and BP-phIDID as a dopant in the emitting layer show highly efficient electroluminescence with maximum external quantum efficiencies of 20.8% and 13.9%, respectively.