Abstract

AbstractRational manipulation of frontier orbital distribution and singlet‐triplet splitting is crucial to exploit the luminescent properties of organic molecules. To realize ultra‐blue luminescence, both blue‐shifted wavelength peak (λpeak) and narrow full‐width at half‐maximum (FWHM) are required. Herein, a new thermally activated delayed fluorescence (TADF) skeleton by inserting the diphenyl methylene intramolecular‐lock to adjust the torsion angles and restrict the intramolecular relaxation is developed. Two rigid emitters, incorporating phenoxazine (PXZN‐B) and acridine (DMACN‐B) as donors and mesitylboron as an acceptor, exhibit narrow FWHMs (<50 nm) with deep‐blue (0.133, 0.147) and violet‐blue emission (0.151, 0.045), respectively. In particular, the Commission Internationale de l'Eclairage (CIE) coordinates of a DMACN‐B‐based device closely approach the Rec.2020 standard (0.131, 0.046). Moreover, both of the organic light‐emitting diodes (OLEDs) based on PXZN‐B and DMACN‐B show TADF character, with high external quantum efficiencies (EQEs) exceeding 10%. Furthermore, owing to the large orbital overlap, these TADF emitters own a fast S1–S0 transition rate exceeding 108 s–1, thereby exhibiting marked amplified spontaneous emission (ASE) with low thresholds. Therefore, the intramolecular‐lock strategy provides not only innovation for realizing high‐efficiency deep‐blue TADF emission with high color purity but also an avenue for a TADF‐based ASE and lasing application.

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