NDLI: Structural Changes and Coordinatively Unsaturated Metal Atoms on Dehydration of Honeycomb Analogous Microporous Metal

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Structural Changes and Coordinatively Unsaturated Metal Atoms on Dehydration of Honeycomb Analogous Microporous Metal–Organic Frameworks

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Dietzel, Pascal D. C. Blom, Richard Fjellvåg, Helmer Johnsen, Rune E.
Description	Author Affiliation: Dietzel PD ( SINTEF Materials and Chemistry, Department of Hydrocarbon Process Chemistry, PO Box 124 Blindern, 0314 Oslo, Norway. pascal.dietzel@sintef.no)
Abstract	Porous metal–organic framework compounds with coordinatively unsaturated metal sites on the inner surface of the pores promise to be valuable adsorbents and catalyst systems, either in industrial applications or as model systems to study interactions with guest molecules. The dehydration process of two isostructural microporous coordination polymers, $[M_{2}(dhtp)(H_{2}O)_{2}]⋅8 H_{2}O,$ termed CPO-27-M (M=Co, Zn; $H_{4}dhtp=2,5-dihydroxyterephthalic$ acid) was investigated by in situ variable temperature X-ray diffraction. Both compounds contain accessible coordination sites at the metal after complete removal of the solvent. However, despite the analogy of their crystal structures, they behave differently during dehydration. For CPO-27-Co, water desorption is a smooth topotactic process of second order with no concomitant space group change and no increase in microstrain, which is beneficial for the applicability of the material. Removal of the water propagates from the center of the channels outwards. The coordinating water molecule at the metal desorbs only when almost all the bulk water in the pores has disappeared. In contrast, discontinuities in the powder pattern of CPO-27-Zn indicate the occurrence of first-order transitions. The crystal structures of four of the five individual phases could be determined. The structure of the intermediate phase occurring just before the framework is completely evacuated was elusive in respect to full structure solution and refinement, but it is most probably related to the removal of the axis of threefold symmetry. The zinc-based material experiences a significant amount of strain.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	8
Volume Number	14
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2008-01-01
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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