Combined Skeleton and Spatial Rigidification of AIEgens in 2D Covalent Organic Frameworks for Boosted Fluorescence Emission and Sensing of Antibiotics

AIEgens show relatively weak fluorescence performance owing to the existence of π-π interlayer accumulation, molecular layer planarization, and intramolecular rotation in aggregation-induced emission (AIE) molecules, which limit its application scope. Herein, we put forward a combined skeleton and spatial rigidification method to boost the fluorescence emission efficiency of AIEgens. As a proof-of-concept experiment, two highly fluorescent covalent organic frameworks (COFs) were designed and constructed by the Knoevenagel condensation reaction. The experimental results show that the combined skeleton and spatial rigidification endowed excellent fluorescence emission for the resulting F-COF-2 by destruction of the π-π interlayer accumulation, interference of the molecular layer planarization, and restriction of the intramolecular rotation of the AIEgen unit. F-COF-2 displayed highly sensitive and selective NFT and NZF detection. Particularly, the K_sv value and limit of detection of F-COF-2 toward NFT were estimated to be 9.12 × 10⁵ M^-1 and 3.35 ppb, respectively, which surpassed all the reported crystalline porous fluorescent materials. The mechanism study proved that its outstanding fluorescence detection property was ascribed to the formation of a nonfluorescent complex induced by hydrogen bond interactions and electron transfer between F-COF-2 and NFT and NZF. This work not only proposes a combined skeleton and spatial rigidification strategy to improve the fluorescence efficiency of AIE molecules but also develops a sensor with high fluorescence efficiency, high chemical stability, and highly efficient detection of antibiotics.