Thermally-triggered crystal dynamics and permanent porosity in the first heptatungstate-metalorganic three-dimensional hybrid framework

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dc.contributor.authorMartín Caballero, Jagoba
dc.contributor.authorArtetxe, Beñat
dc.contributor.authorReinoso, Santiago
dc.contributor.authorSan Felices, Leire
dc.contributor.authorCastillo, Óscar
dc.contributor.authorBeobide, Garikoitz
dc.contributor.authorVilas, José Luis
dc.contributor.authorGutiérrez Zorrilla, Juan M.
dc.contributor.departmentInstitute for Advanced Materials and Mathematics - INAMAT2en
dc.date.accessioned2024-09-02T16:07:04Z
dc.date.available2024-09-02T16:07:04Z
dc.date.issued2017
dc.date.updated2024-09-02T14:56:14Z
dc.description.abstractThe hybrid compound [{Cu(cyclam)}3(W7O24)]⋅15.5 H2O (1) (cyclam=1,4,8,11-tetraaza-cyclotetradecane) was synthesized by reacting the {Cu(cyclam)}2+ complex with a tungstate source in water at pH 8. Compound 1 exhibits an unprecedented three-dimensional covalent structure built of heptatungstate clusters linked through metalorganic complexes in a POMOF-like framework that displays water-filled channels. This dynamic architecture undergoes two sequential single-crystal-to-single-crystal transformations upon thermal evacuation of water molecules to result in the partially dehydrated [{Cu(cyclam)}3(W7O24)]⋅12 H2O (2) and anhydrous [Cu(cyclam)]0.5[{Cu(cyclam)}2.5(W7O24)] (3) crystalline phases. These transitions are associated with cluster rotations and modifications in the CuII coordination geometries, which reduce the dimensionality of the original lattice to layered systems but preserving the porous nature. Phase 3 reverts to 2 upon exposure to ambient moisture, whereas the transition between 1 and 2 proved to be irreversible. The permanent microporosity of 3 was confirmed by gas sorption measurements (N2, CO2), which reveal a system of parallel channels made of wide cavities connected through narrow necks that limit the adsorption process. This observation is in good agreement with Grand Canonical Monte Carlo simulations.en
dc.description.sponsorshipThis work was funded by UPV/EHU (Grant PPG17/37). S.R. acknowledges financial support from InaMat and from the program “Ayudas para la Captación del Talento Adscritas a los Institutos de Investigación de la UPNA” funded by a collaboration agreement with Obra Social la Caixa and Fundación Caja Navarra.
dc.format.mimetypeapplication/pdfen
dc.identifier.citationMartín-Caballero, J., Artetxe, B., Reinoso, S., San Felices, L., Castillo, O., Beobide, G., Vilas, J.L., Gutiérrez-Zorrilla, J.M. (2017) Thermally-triggered crystal dynamics and permanent porosity in the first heptatungstate-metalorganic three-dimensional hybrid framework. Chemistry - A European Journal, 23(59), 14962-14974. https://doi.org/10.1002/chem.201703585.
dc.identifier.doi10.1002/chem.201703585
dc.identifier.issn0947-6539
dc.identifier.urihttps://academica-e.unavarra.es/handle/2454/51526
dc.language.isoeng
dc.publisherWiley
dc.relation.ispartofChemistry - A European Journal, 2017, 23(59), 14962-14974
dc.relation.publisherversionhttps://doi.org/10.1002/chem.201703585
dc.rights© 2017 Wiley-VCH Verlag
dc.rights.accessRightsinfo:eu-repo/semantics/openAccess
dc.subjectPolyoxometalatesen
dc.subjectSCSC transformationsen
dc.subjectGas sorptionen
dc.subjectX-ray diffractionen
dc.subjectSupramolecular chemistryen
dc.titleThermally-triggered crystal dynamics and permanent porosity in the first heptatungstate-metalorganic three-dimensional hybrid frameworken
dc.typeinfo:eu-repo/semantics/article
dc.type.versioninfo:eu-repo/semantics/acceptedVersion
dspace.entity.typePublication
relation.isAuthorOfPublication46bbf241-764d-4c78-9667-4c307cf84092
relation.isAuthorOfPublication.latestForDiscovery46bbf241-764d-4c78-9667-4c307cf84092

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