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In this study, a dysprosium-based metal–organic framework (MOF) sensor (Dy-MOF) was developed for the ratiometric detection of I− in aqueous medium. Upon excitation at 230 nm, Dy-MOF shows two dominant emission bands at 464 nm and 574 nm assigned to (4F, 4D)5/2 → 6H9/2 + 6F11/2 and 4F9/2 → 6H13/2 transition of Dy3+, respectively, which have different sensitivities toward iodide ions. The introduction of I− slightly weakened the blue emission at 464 nm and significantly quenched the yellow emission at 574 nm. Thus, ratiometric sensing for iodide was realized using the yellow-to-blue intensity ratio of Dy3+. Dy-MOF exhibits superior sensing behavior towards I− with high selectivity, sensitivity and low detection limit (24 nM). This study also provides a strategy for the construction of a ratiometric sensor with dual-emission bands originating from only one emission center. [ABSTRACT FROM AUTHOR]

Detection of Fe(III) and Cu(II) in water is highly desirable because their abnormal levels can cause serious harm to human health and environmental safety. In this work, a ratiometric luminescence sensing platform based on lanthanide-based silica nanoparticles was constructed for the detection of Fe3+ and Cu2+ ions. The terbium-silica nanoparticles (named SiO2@Tb) with dual-emission signals were successfully prepared by grafting Tb3+ ions onto trimellitic anhydride (TMA) functionalized silica nanospheres. It can serve as a ratiometric fluorescent probe for the detection of Fe3+ and Cu2+ ions in water with the green emission of Tb3+ ions as a response signal and the blue emission of silica nanospheres as the reference signal. Significantly, an easy-to-differentiate color change for visual detection was also realized. SiO2@Tb shows high sensitivity even in very low concentration regions towards the sensing of Fe3+ and Cu2+ with low detection limits of 0.75 μM and 0.91 μM, respectively. Moreover, the mechanism for the luminescence quenching of SiO2@Tb was systematically investigated, and was attributed to the synergetic effect of the absorption competition quenching (ACQ) mechanism and cation exchange. This study demonstrates that SiO2@Tb can be employed as a promising fluorescent probe for the detection of Fe3+ and Cu2+ ions, and the combination of lanthanide ions with silica nanoparticles is an effective strategy to construct a ratiometric fluorescent sensing platform for the determination of analytes in environmental detection. [ABSTRACT FROM AUTHOR]

A luminescence sensor based on an europium(III)-based lanthanide–organic framework, [Eu(BCB)(DMF)]·(DMF)1.5(H2O)2 (1), was synthesized via a solvothermal method using 4,4′,4′′-benzenetricarbonyltribenzoic acid (H3BCB) as a bridging ligand. Single-crystal X-ray diffraction indicates that Eu centers are eight-coordinated with a trigonal dodecahedron and a square antiprismatic configuration, and adjacent Eu atoms are bridged by BCB organic linkers to form a 3D rod-packing structure. Photoluminescence studies show that compound 1 emits bright red luminescence and behaves as a multi-responsive luminescent sensor toward 4-nitrophenol (4-NP) and I− and Fe3+ ions in water with high sensitivity, selectivity and low detection limits. Furthermore, the possible luminescence sensing mechanisms were also investigated by PXRD analysis, UV-vis spectroscopy and X-ray photoelectron spectroscopy (XPS). The recognition mechanism for 4-NP and I− ions can be attributed to the competition absorption and that for Fe3+ ions is considered to be a multi-quenching mechanism dominated by competition absorption. This study demonstrates that the lanthanide-based MOF might be a promising candidate for the detection of 4-NP and I− and Fe3+ ions in aqueous medium. [ABSTRACT FROM AUTHOR]

Detection of Fe(III) and Cu(II) in water is highly desirable because their abnormal levels can cause serious harm to human health and environmental safety. In this work, a ratiometric luminescence sensing platform based on lanthanide-based silica nanoparticles was constructed for the detection of Fe 3+ and Cu 2+ ions. The terbium-silica nanoparticles (named SiO 2 @Tb) with dual-emission signals were successfully prepared by grafting Tb 3+ ions onto trimellitic anhydride (TMA) functionalized silica nanospheres. It can serve as a ratiometric fluorescent probe for the detection of Fe 3+ and Cu 2+ ions in water with the green emission of Tb 3+ ions as a response signal and the blue emission of silica nanospheres as the reference signal. Significantly, an easy-to-differentiate color change for visual detection was also realized. SiO 2 @Tb shows high sensitivity even in very low concentration regions towards the sensing of Fe 3+ and Cu 2+ with low detection limits of 0.75 μM and 0.91 μM, respectively. Moreover, the mechanism for the luminescence quenching of SiO 2 @Tb was systematically investigated, and was attributed to the synergetic effect of the absorption competition quenching (ACQ) mechanism and cation exchange. This study demonstrates that SiO 2 @Tb can be employed as a promising fluorescent probe for the detection of Fe 3+ and Cu 2+ ions, and the combination of lanthanide ions with silica nanoparticles is an effective strategy to construct a ratiometric fluorescent sensing platform for the determination of analytes in environmental detection.

A luminescence sensor based on an europium(III)-based lanthanide-organic framework, [Eu(BCB)(DMF)]·(DMF) 1.5 (H 2 O) 2 (1), was synthesized via a solvothermal method using 4,4',4''-benzenetricarbonyltribenzoic acid (H 3 BCB) as a bridging ligand. Single-crystal X-ray diffraction indicates that Eu centers are eight-coordinated with a trigonal dodecahedron and a square antiprismatic configuration, and adjacent Eu atoms are bridged by BCB organic linkers to form a 3D rod-packing structure. Photoluminescence studies show that compound 1 emits bright red luminescence and behaves as a multi-responsive luminescent sensor toward 4-nitrophenol (4-NP) and I - and Fe 3+ ions in water with high sensitivity, selectivity and low detection limits. Furthermore, the possible luminescence sensing mechanisms were also investigated by PXRD analysis, UV-vis spectroscopy and X-ray photoelectron spectroscopy (XPS). The recognition mechanism for 4-NP and I - ions can be attributed to the competition absorption and that for Fe 3+ ions is considered to be a multi-quenching mechanism dominated by competition absorption. This study demonstrates that the lanthanide-based MOF might be a promising candidate for the detection of 4-NP and I - and Fe 3+ ions in aqueous medium.