Intra-Ionic Dual Excited-State Emissions of Micelle-Encapsulated Eu(III) for Metal-Ion Sensing Map
Mengfei Wang1,2, Taichi Inoshita3, Toranosuke Tomikawa3
1Faculty of Engineering, Hokkaido University, Sapporo, Hokkaido, Japan.
Abstract:
Current lanthanide-based ratiometric luminescence sensing typically relies on ground-state splitting of lanthanide ions or dual-component systems. Herein, a conceptually distinct strategy utilizing the intrinsic excited-state diversity of the trivalent europium ion (Eu(III)) is introduced for aqueous ratiometric metal-ion sensing. By encapsulating a rigid [Eu(hfa)3(dppy)2] (hfa: hexafluoroacetylacetonate; dppy: 4-pyridyldiphenylphosphine oxide) complex within micellar environments, the emissions from the dominant 5D0 and the higher-lying 5D1 states of Eu(III) are successfully preserved in aqueous media. Using the distinct susceptibility of these two emitting excited states to non-radiative deactivation pathways induced by metal-ion coordination [Eu(hfa)3(dppy)2] exhibits differential quenching responses to varying divalent metal-ions (Mn, Fe, Co, Ni, Cu). This allows for the construction of a unique ratiometric metal-ion sensing map. This study demonstrates the first Eu(III)-based system employing intra-ionic excited-state diversity for discrimination, offering a robust, self-referenced sensing platform.
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