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Sur la mise en oeuvre de composés de coordination tétraédriques pour l'élaboration d'architectures supramoléculaires nanoporeuses : synthèse, caractérisation et propriétés zéolitiques d'édifices hétérométalliques ou hybrides

Abstract : The preparation of micro-porous metal-organic frameworks has been envisaged by assemblage of pre-formed tetrahedral coordination compounds involved as primary building units. A typical example of such a building block is (M(oxalate)4)4- (with M = UIV, ZrIV, etc...) but the tetrahedral (Zr(chloranilate)4)4- and (Zr(dihydrobenzoquinolate)4)4- complexes have been envisaged as well. Their assemblage with either metal ions by the means of coordination bonds or organic cations through charge-assisted H-bond lead to a series of structurally characterized 2-D and 3-D supramolecular nano-porous architectures. This approach permitted the synthesis of rare examples of heterometallic open frameworks. These structures display channels with apertures up to 12 Å x 8 Å which are emptied from solvates at mild temperatures without affecting the chemical scaffolds which integrity is maintained up to 250-300°C. A certain degree of flexibility of the coordination polymers upon guest release is suggested by the temperature dependence of the powder X-ray patterns and N2 sorption experiments, but reversible and selective sorption of small molecules has been observed suggesting these open-frameworks to behave like sponges. The flexibility of the framework upon guest release is illustrated by the crystal structures of the hydrated and dehydrated phases of [K4(Zr(dhbq)4)] (dhbq = dihydrobenzoquinolate). Finally, the different sorption measurements (BET, Langmuir) show that these supramolecular porous materials are promising adsorbents; preliminary results show that they might be envisaged for hydrogen.
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https://tel.archives-ouvertes.fr/tel-00010844
Contributor : Stéphane Toulin <>
Submitted on : Monday, October 31, 2005 - 5:39:10 PM
Last modification on : Saturday, March 30, 2019 - 1:38:59 AM
Long-term archiving on: : Friday, April 2, 2010 - 10:23:52 PM

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  • HAL Id : tel-00010844, version 1

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Inhar Imaz. Sur la mise en oeuvre de composés de coordination tétraédriques pour l'élaboration d'architectures supramoléculaires nanoporeuses : synthèse, caractérisation et propriétés zéolitiques d'édifices hétérométalliques ou hybrides. Matériaux. Université Sciences et Technologies - Bordeaux I, 2005. Français. ⟨tel-00010844⟩

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