A Dy(III) Coordination Polymer Material as a Dual-Functional Fluorescent Sensor for the Selective Detection of
Ying Wang1, Baigang An1, Si Li2
1Key Laboratory of Energy Materials and Electrochemistry Research Liaoning Province, School of Chemical Engineering, University of Science and Technology Liaoning, Anshan 114051, China.
Abstract:
A Dy(III) coordination polymer (CP), [Dy(spasds)(H2O)2]n (1) (Na2Hspasds = 5-(4-sulfophenylazo)salicylic disodium salt), has been synthesized using a hydrothermal method and characterized. 1 features a 2D layered structure, where the spasda3- anions act as pentadentate ligands, adopting carboxylate, sulfonate and phenolate groups to bridge with four Dy centers in η3-μ1: μ2, η2-μ1: μ1, and monodentate coordination modes, respectively. It possesses a unique (4,4)-connected net with a Schläfli symbol of {44·62}{4}2. The luminescence study revealed that 1 exhibited a broad fluorescent emission band at 392 nm. Moreover, the visual blue color has been confirmed by the CIE plot. 1 can serve as a dual-functional luminescent sensor toward Fe3+ and MnO4- through the luminescence quenching effect, with limits of detection (LODs) of 9.30 × 10-7 and 1.19 × 10-6 M, respectively. The LODs are relatively low in comparison with those of the reported CP-based sensors for Fe3+ and MnO4-. In addition, 1 also has high selectivity and remarkable anti-interference ability, as well as good recyclability for at least five cycles. Furthermore, the potential application of the sensor for the detection of Fe3+ and MnO4- was studied through simulated wastewater samples with different concentrations. The possible sensing mechanisms were investigated using Ultraviolet-Visible (UV-Vis) absorption spectroscopy and density functional theory (DFT) calculations. The results revealed that the luminescence turn-off effects toward Fe3+ and MnO4- were caused by competitive absorption and photoinduced electron transfer (PET), and competitive absorption and inner filter effect (IFE), respectively.
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