Integrating the atomically separated frontier molecular orbital distribution of two multiple resonance frameworks...

Atomically separated frontier molecular orbital (FMO) distribution plays a crucial role in achieving narrowband emissions for multiple resonance (MR)-type thermally activated delayed fluorescence emitters. Directly peripherally decorating a MR framework with donor or acceptor groups is a common strategy for developing MR emitters. However, this approach always induces bonding features and thus spectral broadening as a side effect. How direct donor/acceptor decoration enhances atomic FMO separation while avoiding bonding features has not been explored. For this aim, two MR derivatives are synthesized by integrating two MR frameworks at different sites. Following resonance alignment, DOBNA-m-CzBN avoids breaking nonbonding FMO features at the single connecting bond and shows enhanced MR characteristics, with a sharp emission at 491 nm and a full width at half maximum (FWHM) of 24 nm/118 meV. Conversely, DOBNA-p-CzBN emerges as a bonding feature due to its continuous π-conjugation extension, with a broadened FWHM of 26 nm/132 meV peaking at 497 nm. Impressively, both emitters exhibit outstanding external quantum efficiencies of 37.8-38.6% in organic light-emitting diodes (OLEDs), demonstrating improved performance with rigid acceptor decoration. Distinctly, the electroluminescence of DOBNA-m-CzBN shows a narrower FWHM than that of DOBNA-p-CzBN. This work for the first time reports the enhancement of atomic FMO separation for MR emitters via peripheral decoration through a single bond and provides a more comprehensive illustration for further development of MR emitters.