4.6 Article

Structural changes and coordinatively unsaturated metal atoms on dehydration of honeycomb analogous microporous metal-organic frameworks

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CHEMISTRY-A EUROPEAN JOURNAL
卷 14, 期 8, 页码 2389-2397

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WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200701370

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coordination polymers; microporous materials; single-site catalyst; topotactic transformation; X-ray diffraction

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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)-(H2O)(2)]center dot 8H(2)O, termed CPO-27-M (M=Co, Zn; H(4)dhtp=2,5-dihydroxytereplithalic 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.

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