With increasing global industrialization, it is urgent and challenging to develop multifunctional species for detection and adsorption in the environment. For this purpose, a novel anionic heterometallic organic framework, [(CH)NH][CaEu(CAM)(HO)]·4HO·4DMF (), is hydrothermally synthesized based on chelidamic acid (HCAM). Single crystal analysis shows that features two different oxygen-rich channels along the -axis in which one CAM bridges two sextuple-coordinated Ca and two octuple-coordinated Eu with a μ-η: η: η: η: η: η new chelating and bridging mode. The characteristic bright red emission and superior hydrostability of under harsh acidic and basic conditions benefit it by acting as a highly sensitive sensor for Fe and 3-nitrophenol (3-NP) with extremely low LODs through remarkable quenching. The combination of experiments and theoretical calculations for sensing mechanisms shows that the competitive absorption and interaction are responsible for Fe-induced selective emission quenching, while that for 3-NP is the result of the synergism of host-guest chemistry and the inner filter effect. Meanwhile, the assimilation of negative charge plus channels renders a highly selective adsorbent for methylene blue (MB) due to a synergy of electrostatic affinity, ion-dipole interaction, and size matching. Of note is the reusability of toward Fe/3-NP sensing and MB adsorption besides its fast response. These findings could be very useful in guiding the development of multifunctional Ln-MOFs for sensing and adsorption applications in water media.

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