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Rare-Earth Perhalogenated Terephthalate Metal-Organic Frameworks: Fluorescence Sensors for Iron, Copper, and Nitroaromatic Explosives Jermaine A. Smith* 1 , Marvadeen A. Singh-Wilmot 2 , Korey P. Carter 3 , Christopher L. Cahill 4 , James A. Ridenour 5 1,2 Department of Chemistry, The University of the West Indies, Mona, Kingston, Jamaica 3,4,5 Department of Chemistry, The George Washington University, Washington, USA Metal-Organic Frameworks (MOFs) are a new class of porous coordination polymers (CPs) with well- defined topologies that continue to intrigue scientists not only because of their appealing structural architectures, but also because of their potential applications in gas storage and separation, sensing of small molecules, catalysis and biomedicine (Cui, et al., 2012). The synthesis of MOFs using rare earth (RE) ions is still relatively under explored when compared to transition metal-based systems, due to their unpredictable coordination chemistry. There are however significant advantages to be gained by combining the unique catalytic, magnetic and light emitting properties of RE ions with the properties of CPs and MOFs (Singh-Wilmot et al., 2017; Smith et al., 2016; Min et al., 2012). By reacting rare-earth ions with tetrafluoro- and tetrabromo-terephthalate ligands under slow evaporation conditions, we have been able to create 28 novel rare-earth CPs and MOFs having interesting structural features and promising luminescence sensing properties. We demonstrate the potential of these compounds as fluorescence sensors for Fe3+, Cu2+, and explosive nitroaromatic compounds (NACs) such as 4-nitro-, 2,4-dinitro- and 2,4,6-trinitro-phenol.
Keywords: Rare-Earth Metals; Metal-Organic Frameworks; Coordination Polymers; Fluorescence Sensors; Perhalogenated Terephthalate Ligands; Nitroaromatic Explosives References: 1. Cui, Y., Yue, Y., Qian, G., and Chen, B. (2012), “Luminescent functional metal-organic frameworks”, Chemical Reviews , Vol.112, No.2, pp.1126-1162. 2. Singh-Wilmot, M. A., Sinclair, R. A., Kahwa, I. A., and Lough, A. J. (2017), “Eu 3+ substitutional defects and their effect on the luminescence spectral and decay dynamics of sal-type one dimensional rare earth coordination polymers and trinuclear complexes”, Journal of Luminescence , Vol.182, pp.98-106. 3. Smith, J. A., Singh-Wilmot, M. A., Carter, K.P., Cahill, C.L., Lough, A.J., and Knee, C.S. (2016), “Eight rare earth metal organic frameworks and coordination polymers from 2-nitroterephthlate: syntheses, structures, solid-state luminescence and an unprecedented topology”, New Journal of Chemistry , Vol.40, No.9, pp.7338-7349. 4. Min, Z., Singh-Wilmot, M.A., Cahill, C.L., Andrews, M., and Taylor, R. (2012), “Isoreticular lanthanide metal-organic frameworks: Syntheses, structures and photoluminescence of a family of 3D phenylcarboxylates”, European Journal of Inorganic Chemistry , Vol.28, pp.4419-4426. 5. Section of Conference: Energy and Materials
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