Organic room-temperature phosphorescence, a spin-forbidden radiative process, has emerged as an interesting but rare phenomenon with multiple potential applications in optoelectronic devices, biosensing and anticounterfeiting. Covalent organic frameworks (COFs) with accessible nanoscale porosity and precisely engineered topology can offer unique benefits in the design of phosphorescent materials, but these are presently unexplored. Here, we report an approach of covalent doping, whereby a COF is synthesized by copolymerization of halogenated and unsubstituted phenyldiboronic acids, allowing for random distribution of functionalized units at varying ratios, yielding highly phosphorescent COFs. Such controlled halogen doping enhances the intersystem crossing while minimizing triplet–triplet annihilation by diluting the phosphors. The rigidity of the COF suppresses vibrational relaxation and allows a high phosphorescence quantum yield (Φ_Phos ≤ 29%) at room temperature. The permanent porosity of the COFs and the combination of the singlet and triplet emitting channels enable a highly efficient COF-based oxygen sensor, with an ultra-wide dynamic detection range (~10³–10⁻⁵ torr of partial oxygen pressure).

有机室温磷光是一种自旋禁止的辐射过程，已成为一种有趣但罕见的现象，在光电器件、生物传感和防伪方面具有多种潜在应用。具有可接近的纳米级孔隙率和精确设计的拓扑结构的共价有机骨架 (COF) 可以在磷光材料的设计中提供独特的优势，但这些目前尚未得到探索。在这里，我们报告了一种共价掺杂的方法，通过共聚卤化和未取代的苯基二硼酸合成 COF，允许功能化单元以不同的比例随机分布，从而产生高磷光 COF。这种受控的卤素掺杂增强了系统间的交叉，同时通过稀释荧光粉最大限度地减少了三重态-三重态湮灭。Φ _Phos  ≤ 29%) 在室温下。COF 的永久孔隙率以及单线态和三线态发射通道的组合使基于 COF 的高效氧传感器具有超宽动态检测范围（~10 ³ –10 ^-5 托的氧分压）。