Function‐Targeted Lanthanide‐Anchored Polyoxometalate–Cyclodextrin Assembly: Discriminative Sensing of Inorganic Phosphate and Organophosphate

Abstract Polyoxometalate (POM) clusters containing lanthanide ion (LnPOM) possess excellent luminescence features, but the envisaged applications are hindered by the challenges in integration into functional architectures. Herein, a novel cross‐linked cyclodextrin (CL‐CD) and LnPOM composite is developed and applied for discriminative detection of inorganic and organic phosphate phases. For inorganic phosphates, a ratiometric fluorescence response is demonstrated with excellent selectivity, and anti‐interference ability in complex analyte mixtures. The outstanding performance is attributed to the high affinity of POM and distinct interactions between La 3+ and Eu 3+ with the phosphate. For organophosphates, a “signal‐off” fluorescence response for p ‐nitrophenyl‐substituted organophosphates is discovered due to the encapsulation of nitrophenyl group into the hydrophobic cavity of CD that enhances the interactions between POM and p ‐nitrophenyl phosphate. The discriminative responses of CL‐CD–LnPOM to inorganic phosphates and organophosphates bring new insights into POM‐based fluorescence probes for the detection of inorganic and organic phases based on the intrinsic structural difference between the phosphate analogs.