DOI: 10.1002/chem.200701370. Structural Changes and Coordinatively Unsaturated Metal Atoms on Dehydration of Honeycomb Analogous Microporous Metal

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

10.1002/chem.200701370

Crossref journal-article

Wiley

Chemistry – A European Journal (311)

Abstract

AbstractPorous 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, [M2(dhtp)(H2O)2]⋅8 H2O, termed CPO‐27‐M (M=Co, Zn; H4dhtp=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.

Bibliography

Dietzel, P. D. C., Johnsen, R. E., Blom, R., & FjellvÃ¥g, H. (2008). Structural Changes and Coordinatively Unsaturated Metal Atoms on Dehydration of Honeycomb Analogous Microporous MetalâOrganic Frameworks. Chemistry â A European Journal, 14(8), 2389â2397. Portico.

Authors 4

Pascal D. C. Dietzel (first)
Rune E. Johnsen (additional)
Richard Blom (additional)
Helmer Fjellvåg (additional)

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Dates

Type	When
Created	17 years, 7 months ago (Jan. 18, 2008, 5:53 a.m.)
Deposited	1 year, 10 months ago (Oct. 16, 2023, 12:22 p.m.)
Indexed	13 hours, 56 minutes ago (Aug. 21, 2025, 12:54 p.m.)
Issued	17 years, 5 months ago (Feb. 28, 2008)
Published	17 years, 5 months ago (Feb. 28, 2008)
Published Online	17 years, 5 months ago (Feb. 28, 2008)
Published Print	17 years, 5 months ago (March 7, 2008)

Funders 0

None

BibTeX

@article{Dietzel_2008, title={Structural Changes and Coordinatively Unsaturated Metal Atoms on Dehydration of Honeycomb Analogous Microporous Metal–Organic Frameworks}, volume={14}, ISSN={1521-3765}, url={http://dx.doi.org/10.1002/chem.200701370}, DOI={10.1002/chem.200701370}, number={8}, journal={Chemistry – A European Journal}, publisher={Wiley}, author={Dietzel, Pascal D. C. and Johnsen, Rune E. and Blom, Richard and Fjellvåg, Helmer}, year={2008}, month=feb, pages={2389–2397} }

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