<p>A novel strategy is presented for constructing ratiometric fluorescent detection platform based on terbium(Ⅲ) ion as a single luminescence center, enabling sensing of permanganate ions (MnO<sub>4</sub><sup>‒</sup>) in water. The approach leverages the differential quenching mechanisms of MnO<sub>4</sub><sup>‒</sup> on distinct emission bands of terbium-based metal-organic frameworks (Tb-MOFs), using the intensity ratio of specific emission wavelengths (I<sub>548</sub>/I<sub>622</sub>) as the detection signal for MnO<sub>4</sub><sup>‒</sup> quantification. A ratiometric probe [Tb(BCB)(DMF)]<b>·</b>(DMF)<sub>1.5</sub>(H<sub>2</sub>O)<sub>2</sub> (H<sub>3</sub>BCB: 4,4’,4’’-benzenetricarbonyltribenzoic acid) (<b>1</b>) was developed, demonstrating high selectivity, sensitivity, and anti-interference capability toward MnO<sub>4</sub><sup>‒</sup>. The study of quenching mechanism reveals that the 622&#xa0;nm emission is quenched solely by the inner filter effect (IFE), whereas the 548&#xa0;nm emission undergoes synergistic quenching by IFE and Förster resonance energy transfer (FRET). This differential quenching leads to a distinct decrease in I<sub>548</sub>/I<sub>622</sub>, forming a robust ratiometric sensing platform. Notably, the method eliminates interference from dichromate ions (Cr<sub>2</sub>O<sub>7</sub><sup>2‒</sup>). The strategy’s generality is validated by a second Tb-MOF ([Tb(cpia)(H<sub>2</sub>O)<sub>2</sub>]<sub>n</sub>·nH<sub>2</sub>O (H<sub>3</sub>cpia: 5-(4-carboxyphenoxy) isophthalic acid) (<b>2</b>)), which also functions as a ratiometric probe for MnO<sub>4</sub><sup>‒</sup>. These findings establish a universal design principle for constructing single-luminescence-center ratiometric fluorescence platforms.</p> Graphical Abstract <p></p>

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Construction of a ratiometric fluorescent detection platform based on dual emission bands of terbium(Ⅲ) ion for sensing of MnO4

  • Runtian Huang,
  • Xiaoming Shen,
  • Qingzhong Guo,
  • Jiangyu Wu,
  • Junfang Guo,
  • Huaming Zheng

摘要

A novel strategy is presented for constructing ratiometric fluorescent detection platform based on terbium(Ⅲ) ion as a single luminescence center, enabling sensing of permanganate ions (MnO4) in water. The approach leverages the differential quenching mechanisms of MnO4 on distinct emission bands of terbium-based metal-organic frameworks (Tb-MOFs), using the intensity ratio of specific emission wavelengths (I548/I622) as the detection signal for MnO4 quantification. A ratiometric probe [Tb(BCB)(DMF)]·(DMF)1.5(H2O)2 (H3BCB: 4,4’,4’’-benzenetricarbonyltribenzoic acid) (1) was developed, demonstrating high selectivity, sensitivity, and anti-interference capability toward MnO4. The study of quenching mechanism reveals that the 622 nm emission is quenched solely by the inner filter effect (IFE), whereas the 548 nm emission undergoes synergistic quenching by IFE and Förster resonance energy transfer (FRET). This differential quenching leads to a distinct decrease in I548/I622, forming a robust ratiometric sensing platform. Notably, the method eliminates interference from dichromate ions (Cr2O72‒). The strategy’s generality is validated by a second Tb-MOF ([Tb(cpia)(H2O)2]n·nH2O (H3cpia: 5-(4-carboxyphenoxy) isophthalic acid) (2)), which also functions as a ratiometric probe for MnO4. These findings establish a universal design principle for constructing single-luminescence-center ratiometric fluorescence platforms.

Graphical Abstract