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Alkaline-Earth and Aminonicotinate Based Coordination Polymers with Combined Fluorescence/Long-Lasting Phosphorescence and Metal Ions Sensing Response

Abstract

Six novel coordination polymers (CPs) based on alkaline-earth (AE) metal ions and two sorts of aminonicotinate ligands, namely [M(μ-2ani)(μ3-2ani)(μ-DMF)]n [MII = Sr (1) and Ba (2)], {[M(μ-6ani)2(H2O)2]•3H2O}n [MII = Ca (3) and Sr (4)], {[Ca(μ-6ani)2(H2O)2]}n (5) and {[Ba(6ani)2(H2O)3]•7H2O}n (6) [where 2ani = 2-aminonicotinate and 6ani = 6-aminonicotinate] have been synthesized and well characterized. All compounds are firstly built up by AE-carboxylate infinite rods that give compact 2D-layered structures in 1 and 2 but open architectures containing microchannels in the AE-6ani system. Interestingly, the architecture of 3 behaves as a flexible platform that undergoes a spontaneous dehydration to yield compound 5. Structural transition occurring from 3 to 5 has been supported by periodic density functional theory (DFT) calculations and X-ray diffraction data. On its part, compound 6 contains a high amount of solvent molecules which suggests the existence of pores in its structure. A deep study of the optical properties consisting of a detailed experimental characterization and DFT based computational calculations of these compounds support a fascinating photoluminescence performance which entails a bright blue emission accompanied by persistent green afterglows at low temperature, especially for compound 5 as reflected by its lifetime (τ ≈ 1.4 s). In addition to its strong room temperature emission properties, we took advantage of the open yet stable structure of compound 4, to check its viability as a new material sensitive to the presence of solvents and/or transition metal ions, via a significant quenching of the luminescence of 4. Remarkably, 4 is shown to be a particularly selective and efficient sensor for some water soluble pollutants.

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Publication details

The article was received on 08 Mar 2019, accepted on 03 May 2019 and first published on 06 May 2019


Article type: Paper
DOI: 10.1039/C9TC01300H
J. Mater. Chem. C, 2019, Accepted Manuscript

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    Alkaline-Earth and Aminonicotinate Based Coordination Polymers with Combined Fluorescence/Long-Lasting Phosphorescence and Metal Ions Sensing Response

    O. Pajuelo-Corral, A. Rodríguez Diéguez, G. Beobide, S. Perez-Yañez, J. Á. García, E. San Sebastian, J. M. Seco and J. Cepeda, J. Mater. Chem. C, 2019, Accepted Manuscript , DOI: 10.1039/C9TC01300H

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