Excellent Crystallinity and Stability Covalent-Organic Frameworks with High Emission and Anions Sensing.

Covalent-organic frameworks (COFs) are a new class of porous crystalline frameworks with high π-conjugation and periodical skeletons. The highly ordered π-conjugation structures in some COFs allow exciton migration and energy transfer over the frameworks, which leads to good fluorescence probing ability. In this work, two COFs (TFHPB-TAPB-COF and TFHPB-TTA-COF) are successfully condensed via the Schiff base condensation reaction. The intramolecular hydrogen bonds between imine bonds and hydroxyl groups form the excited-state intramolecular proton transfer (ESIPT) strategy. Owing to intramolecular hydrogen bonds in the skeleton, the two COFs show high crystallinity, remarkable stability, and excellent luminescence. The COFs represent a good sensitivity and selectivity to fluoride anions via fluorescence turn-off. Other halogen anions (chloride, bromide, and iodine) and acid anions (nitrate and hydrogen carbonate) remain inactive. These results imply that only fluoride anion is capable of opening the hydrogen bond interaction and hence break the ESIPT strategy. The detection limit toward fluoride anion is down to nanomoles level, ranking the best performances among fluoride anion sensors systems.