Dandelion-like covalent organic frameworks with high-efficiency fluorescence for ratiometric sensing and visual...

Iron ions, one of the most common heavy metal pollutants in industrial waste materials, are continuously actively or passively delivered to the environment. Meanwhile, the importance of Fe³⁺ in biological processes in vivo can not be neglected due to its crucial role in maintaining normal physiological function. Therefore, a ratiometric fluorescence covalent organic framework (TD-COF) was constructed for tracking-by-detection of Fe³⁺. Alkynes-extended 1,3,6,8-tetrakis(4-ethynyl benzaldehyde)-pyrene (TEBPY) with complete planar structure and 2,5-dihydroxyterephthalohydrazide (DHTH) with functional group -OH were selected as the building blocks. The ratiometric fluorescence TD-COF with a dandelion-like structure exhibited its dual emission peaked at 510 nm and 630 nm. It displayed an obvious fluorescence color variation of yellow-red-black in the presence of Fe³⁺. Benefiting from the high luminescent efficiency (QY of 36.4%) and multiple identical binding sites, TD-COF exhibited a wide linear range to Fe³⁺ (0.005-50 μM) with a detection limit of 10.9 nM. Additionally, a smartphone visual sensing platform integrated with TD-COF was developed based on the color transformation and successfully applied to visual smart real-time monitoring Fe³⁺. More surprisingly, the maximum adsorption capacity of TD-COF towards Fe³⁺ was 833.3 mg/g due to the coordination interaction and cationic π-effect. The practicability of the smartphone-integrated ratiometric sensing platform for visual tracking-by-detection of Fe³⁺ was verified by choosing tap water as the actual sample, and the recoveries were calculated to be 98.71-100.88%. This work thus developed COF-based ratiometric sensing of Fe³⁺, which is an attractive candidate for further application in fluorescent sensing and visual monitoring.