Quantum mechanics

Catalysis

Intramolecular force

Photochemistry

Materials science

Nuclear physics

Layer (electronics)

Enol

Molecule

Photoluminescence

Phenoxazine

Physics

Organic chemistry

Optics

Fluorescence

Pharmacology

Excited state

OLED

Medicine

Chemistry

Phenothiazine

Optoelectronics

Moiety

Journal of the American Chemical Society

Developing excited-state intramolecular proton transfer (ESIPT) emitters with high photoluminescence quantum yields (ΦPLs) and long fluorescence lifetimes in solid state remains a formidable challenge. In this study, we integrated the molecular design tactics of thermally activated delayed fluorescence (TADF) into ESIPT molecules with the goals of improving their ΦPLs and increasing their fluorescence lifetimes. Two proof-of-concept molecules, PXZPDO and DMACPDO, were developed by adopting symmetric D-π-A-π-D molecular architectures (where D and A represent donors and acceptors, respectively) featuring electron-donating phenoxazine or a 9,9-dimethyl-9,10-dihydroacridine moiety, an ESIPT core β-diketone, and phenylene π-bridges. Both molecules exhibited sole enol-type forms stabilized by intramolecular hydrogen bonds and exhibited a unique and dynamic ESIPT character that was verified by transient absorption analyses. Endowed with distinct TADF features, PXZPDO and DMACPDO showed high ΦPLs of 68% and 86% in the film state, coupled with notable delayed fluorescence lifetimes of 1.33 and 1.94 μs, respectively. Employing these ESIPT emitters successfully achieved maximum external quantum efficiencies (ηexts) of 18.8% and 23.9% for yellow and green organic light-emitting diodes (OLEDs), respectively, which represent the state-of-the-art device performances for ESIPT emitters. This study not only opens a new avenue for designing efficient ESIPT emitters with high ΦPLs and long fluorescence lifetimes in solid state but also unlocks the huge potential of ESIPT emitters in realizing high-efficiency OLEDs.

De Novo Design of Excited-State Intramolecular Proton Transfer Emitters via a Thermally Activated Delayed Fluorescence Channel