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A Novel Strategy toward Thermally Activated Delayed Fluorescence from a Locally Excited State

Jingyao Chen, Xiaoxiao Xiao, Shuai Li, Yuai Duan, Guo Wang, Yi Liao, Qian Peng, Hongbing Fu, Hua Geng, Zhigang Shuai

2022The Journal of Physical Chemistry Letters54 citationsDOI

Abstract

It is well-known that thermally activated delayed fluorescence (TADF) is always generated from charge-transfer (CT) excited states in donor–acceptor (D–A) systems, which limits its application owing to a slow radiative process and a small stimulated emission cross section. Herein, a design strategy is proposed for realizing TADF from a locally excited (LE) state without a typical donor–acceptor type structure through controlling the intersystem crossing (ISC) and reverse intersystem crossing (RISC) processes between the lowest excited singlet with LE character and higher triplet states. Using this strategy, a boron difluoride derivative is theoretically predicted and experimentally synthesized to exhibit locally excited TADF (LE-TADF) with a fairly large radiative rate of 1.12 × 108 s–1, extremely fast RISC rate of 5.09 × 1010 s–1, and a large stimulated emission cross section of 4.35 × 10–17 cm2, making this a promising organic amplified spontaneous emission (ASE) material. This work might open a new avenue to extend TADF materials, especially TADF laser emitters.

Topics & Concepts

Intersystem crossingExcited stateFluorescenceAcceptorSinglet statePhotochemistryMaterials scienceRadiative transferSpontaneous emissionAtomic physicsChemistryOptoelectronicsLaserPhysicsOpticsCondensed matter physicsOrganic Light-Emitting Diodes ResearchLuminescence and Fluorescent MaterialsLanthanide and Transition Metal Complexes