Preventing undesirable structure flexibility in pyromellitate metal organic frameworks
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Removal of coordinated water molecules from the porous Zn‐pyromellitate metal organic framework Zn5(OH)2(PMA)2(H2O)4 · x H2O (PMA = pyromellitic acid or 1,2,4,5‐benzene tetracarboxylic acid) should generate coordinatively unsaturated metal sites suitable for gas adsorption. However, reports of instability towards dehydration have restricted the study and utility of this MOF. Here we examine in more detail the nature of the structural transformation that occurs upon dehydration. This study reveals that a fully reversible crystalline‐crystalline transformation from a porous to a non‐porous homologue takes place, proceeding through a partially dehydrated intermediate. We show that doping the structure with Ni2+ ions at greater than 30 % prevents structural rearrangement, thereby maintaining porosity, and rendering the material effective for gas (nitric oxide) adsorption applications. These results indicate that doping can be an effective means to increase the utility of otherwise unserviceable structures.
Hayes , O G , Warrender , S J , Cordes , D B , Duncan , M J , Slawin , A M Z & Morris , R E 2020 , ' Preventing undesirable structure flexibility in pyromellitate metal organic frameworks ' , European Journal of Inorganic Chemistry , vol. 2020 , no. 26 , pp. 2537-2544 . https://doi.org/10.1002/ejic.202000322
European Journal of Inorganic Chemistry
Copyright © 2020 The Authors. Published by Wiley‐VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
DescriptionThis project has received funding from: the European Union's Horizon 2020 research and innovation program under grant agreement No 685727; the Engineering & Physical Sciences Research Council (EPSRC) under awards EP/K005499/1 and EP/K039210/1; and the University of St Andrews School of Chemistry.
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