Mengyang Dong, Yushan Zhang, Ziyang Wang, Yaru Gao, Jingyi Shan, Yitong Jiao, Ruizi Li, Wenbo Hu, Huili Ma, Zhongfu An, Long Gu
Organic scintillators that combine high triplet-exciton utilization with rapid radioluminescence are vital for achieving high-resolution dynamic X-ray imaging. Thermally activated delayed fluorescence (TADF) scintillators offer an attractive route to efficient triplet harvesting, yet conventional systems face an intrinsic trade-off between radioluminescence efficiency and decay lifetime. This limitation originates from inherently slow reverse intersystem crossing (RISC), which is difficult to accelerate because minimizing the singlet–triplet energy gap (Δ E ST ) often reduces spin–orbit coupling (SOC). Here, we present a molecular design strategy that overcomes this constraint by simultaneously reducing Δ E ST and enhancing SOC through strengthened hybridization between charge-transfer (CT) and locally excited (LE) states, leading to a hybridized 3 LE/ 3 CT triplet manifold coupled to a predominantly 1 CT singlet state. Guided by this principle, we developed three TADF scintillators by pairing a 2-chloro-7-fluoroquinazoline acceptor with phenoselenazine, phenothiazine, or phenoxazine donors. These scintillators exhibit a high photoluminescence quantum yield of 96.3% and an accelerated RISC rate approaching 10 7 s –1 . Impressively, under X-ray irradiation, they achieve a light yield of 26508 photons M eV –1 and a fast radioluminescence lifetime of 3 μs, enabling both high-resolution static imaging and real-time dynamic radiography. This work provides a generalizable molecular design strategy for developing high-performance TADF scintillators for X-ray imaging.