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Preventing Undesirable Structure Flexibility in Pyromellitate Metal Organic Frameworks
Author(s) -
Hayes Oliver G.,
Warrender Stewart J.,
Cordes David B.,
Duncan Morven J.,
Slawin Alexandra M. Z.,
Morris Russell E.
Publication year - 2020
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202000322
Subject(s) - chemistry , porosity , adsorption , metal organic framework , molecule , oxide , benzene , metal , inorganic chemistry , dehydration , doping , chemical engineering , organic chemistry , biochemistry , engineering , physics , optoelectronics
Removal of coordinated water molecules from the porous Zn‐pyromellitate metal organic framework Zn 5 (OH) 2 (PMA) 2 (H 2 O) 4 · x H 2 O (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 Ni 2+ 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.