<p>Cu(I) halide scintillators have emerged as promising alternatives to conventional X-ray imaging materials, owing to their high luminescence efficiency, structural tunability, and solution processability. Among them, one-dimensional (1D) Cu-I coordination polymers (CPs) not only possess excellent X-ray absorption performance and structural diversity, but also exhibit enhanced stability attributed to their continuous inorganic chain frameworks. However, low radiative efficiency remains a core bottleneck hindering the optoelectronic applications of 1D copper iodide CPs. In this study, ligand halogen engineering is synergistically integrated with the thermally activated delayed fluorescence (TADF) mechanism: halogen electron-withdrawing effects tune the singlet-triplet energy gap (Δ<i>E</i><sub>ST</sub>), while the heavy atom effect boosts orbital coupling, promoting TADF and enabling efficient exciton harvesting. Additionally, the electron-withdrawing property of halogens can further reduce the repulsion between Cu and I, suppressing non-radiative transitions and thereby synergistically enhancing the optical performance and light conversion efficiency of the materials. Herein, two 1D Cu-I CPs were successfully synthesized by introducing different halogen atoms into the ligands: [CuI(3,5-2Cl-py)]<sub><i>n</i></sub> (<b>SC-Cl</b>, where 3,5-2Cl-py = 3,5-dichloropyridine) and [CuI(3,5-2Br-py)]<sub><i>n</i></sub> (<b>SC-Br</b>, where 3,5-2Br-py = 3,5-dibromopyridine). Performance characterizations demonstrate that the light yields of <b>SC-Cl</b> and <b>SC-Br</b> reach 14144.4 and 11005.1 photons MeV<sup>−1</sup>, respectively. The flexible scintillation screens fabricated from these two materials achieve high spatial resolutions of 18.8 and 16.0 lp mm<sup>−1</sup> in X-ray imaging. This work not only provides an effective strategy for optimizing the performance of 1D scintillators but also highlights their potential applications in medical diagnosis and security inspection fields.</p>

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Thermally activated delayed fluorescence-active one-dimensional Cu-I coordination polymers for high-resolution X-ray imaging: tuning the singlet-triplet energy gap through halogen engineering

  • Bao-Yi Li,
  • Wen-Long Zhou,
  • Peng-Kun Wang,
  • Wen-Fei Wang,
  • Rong Li,
  • Shuai-Hua Wang,
  • Fa-Kun Zheng,
  • Guo-Cong Guo

摘要

Cu(I) halide scintillators have emerged as promising alternatives to conventional X-ray imaging materials, owing to their high luminescence efficiency, structural tunability, and solution processability. Among them, one-dimensional (1D) Cu-I coordination polymers (CPs) not only possess excellent X-ray absorption performance and structural diversity, but also exhibit enhanced stability attributed to their continuous inorganic chain frameworks. However, low radiative efficiency remains a core bottleneck hindering the optoelectronic applications of 1D copper iodide CPs. In this study, ligand halogen engineering is synergistically integrated with the thermally activated delayed fluorescence (TADF) mechanism: halogen electron-withdrawing effects tune the singlet-triplet energy gap (ΔEST), while the heavy atom effect boosts orbital coupling, promoting TADF and enabling efficient exciton harvesting. Additionally, the electron-withdrawing property of halogens can further reduce the repulsion between Cu and I, suppressing non-radiative transitions and thereby synergistically enhancing the optical performance and light conversion efficiency of the materials. Herein, two 1D Cu-I CPs were successfully synthesized by introducing different halogen atoms into the ligands: [CuI(3,5-2Cl-py)]n (SC-Cl, where 3,5-2Cl-py = 3,5-dichloropyridine) and [CuI(3,5-2Br-py)]n (SC-Br, where 3,5-2Br-py = 3,5-dibromopyridine). Performance characterizations demonstrate that the light yields of SC-Cl and SC-Br reach 14144.4 and 11005.1 photons MeV−1, respectively. The flexible scintillation screens fabricated from these two materials achieve high spatial resolutions of 18.8 and 16.0 lp mm−1 in X-ray imaging. This work not only provides an effective strategy for optimizing the performance of 1D scintillators but also highlights their potential applications in medical diagnosis and security inspection fields.