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Inorganics 2018, 6(3), 96; https://doi.org/10.3390/inorganics6030096

High-Throughput Synthesis of Pillared-Layered Magnesium Tetraphosphonate Coordination Polymers: Framework Interconversions and Proton Conductivity Studies

1
Faculty of Science & Engineering, University of Wolverhampton, Wulfruna Street, Wolverhamton WV1 1LY, UK
2
Departamento de Química Inorgánica, Universidad de Málaga, Campus Teatinos s/n, 29071 Málaga, Spain
3
Crystal Engineering, Growth and Design Laboratory, Department of Chemistry, University of Crete, Voutes Campus, Crete GR-71003, Greece
4
Institut de Ciència de Materials de Barcelona (CSIC), 08193 Bellaterra, Catalunya, Spain
5
ALBA Synchrotron, Ctra. BP1413 km 3.3, 08290 Cerdanyola del Vallès, Barcelona, Spain
*
Authors to whom correspondence should be addressed.
Received: 8 August 2018 / Revised: 6 September 2018 / Accepted: 7 September 2018 / Published: 11 September 2018
(This article belongs to the Special Issue Metal Phosphates and Phosphonates)
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Abstract

Novel pillared-layered framework materials were synthesized by high-throughput or microwave-assisted methodology that contain Mg2+ and the zwitterionic linker HDTMP (hexamethylenediamine-N,N,N′,N′-tetrakis(methylenephosphonic acid)). Three compounds were structurally characterized by X-ray powder diffraction. In the compound {Mg[(HO3PCH2)2N(CH2)6N(CH2PO3H2)2]·(H2O)}n(1), obtained at 140 °C by hydrothermal or microwave-assisted reaction, the layers are built by isolated Mg2+ octahedra coordinated by oxygen atoms from six different zwitterionic HDTMP ligands. Each amino-bis(methylenephosphonate) moiety links three Mg2+ ions, bridging two of them through one phosphonate group and connecting the third polyhedron in a monodentate fashion. In Compound 2, {Mg[(HO3PCH2)2N(CH2)6N(CH2PO3H2)2]}n, hydrothermally synthesized at 180 °C, the layers are composed of bidentate amino-bis(methylenephosphonate) moieties connected to three Mg2+ ions, with one of the phosphonate groups acting as a bridging ligand. Various subtle structural changes are noted for the other two compounds. Thermodiffraction of 1 reveals that a crystalline-to-crystalline phase transformation occurs concomitantly with its dehydration, leading to a new anhydrous phase, namely, {Mg[(HO3PCH2)2N(CH2)6N(CH2PO3H2)2]}n(1deh). This process is fully reversible upon equilibrating the solid at room temperature. The reported compounds can adsorb ammonia and CO2. Compound 1 exhibits a moderate proton conductivity, ~1.5 × 10−5 S·cm−1 at 80 °C and 95% RH, that increases a half order of magnitude after experiencing a complete dehydration/rehydration process, 11deh1. View Full-Text
Keywords: proton conductivity; coordination polymers; metal phosphonates; tetraphosphonates; gas adsorption; dehydration/rehydration proton conductivity; coordination polymers; metal phosphonates; tetraphosphonates; gas adsorption; dehydration/rehydration
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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Colodrero, R.M.; Salcedo, I.R.; Bazaga-García, M.; Barouda, E.; Papadaki, M.; Papathanasiou, K.E.; Hernández-Alonso, D.; Rius, J.; Aranda, M.A.; Losilla, E.R.; Olivera-Pastor, P.; Demadis, K.D.; Cabeza, A. High-Throughput Synthesis of Pillared-Layered Magnesium Tetraphosphonate Coordination Polymers: Framework Interconversions and Proton Conductivity Studies. Inorganics 2018, 6, 96.

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