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Design of lanthanide metal organic frameworks incorporating dicarboxylate ligands

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Abstract

The combination under mild and solvo/hydrothermal condition of isophtalate (iso), oxalate (ox) and fumarate (fum) acid with lanthanide salts of La, Ce and Gd leads to the formation in crystalline state, of diverse dimensionality frameworks. The structures of four new metal organic frameworks, determined by single crystal X-ray diffraction, exhibit three different coordination patterns. [Gd2(iso)3(H2O)8]∙2(dmf)∙6H2O (1) (dmf = dimethylformamide) develops a 1D ribbons structure containing rectangular shaped channels filled with water and dmf solvents described by a 3-connected SP 1-periodic net (4,4)(0,2) topology. Compound {K[Gd2(iso)3(ox)(H2O)3]}∙(Hdma)∙H2O (2) ([Hdma]+ = [(CH3)2NH2]+) is an anionic 3D heterometallic framework constructed by mixed iso and ox ligands in diverse coordination modes leading to 1D open channels in which [Hdma]+ and water species are located. This network displays an unprecedented 2,3,14-c connected topology. 3D framework has been also observed for isotructural compounds [La2(fum)2(ox)(H2O)4]∙4H2O (3) and [Ce2(fum)2(ox)(H2O)4]∙4H2O (4) constructed by Ln–μ4–fumarate layers (Ln = La, Ce) interconnected by μ2–oxalate ligand forming intersected channels occupied by guest water molecules. These laters are also isostructural analogues of succinate series. The topological analysis of this network results in a binodal 4,5-c net with a 4,5T12 topology having Schläfli symbol of {44.62}{44.64.82}.

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  1. Laboratoire des Sciences des Matériaux et de l’Environnement, Faculté des Sciences de Sfax, Université de Sfax, BP 1171, 3000, Sfax, Tunisia

    Firas Krichen, Siwar Walha & Ahlem Kabadou

  2. LUNAM Université, Université du Maine, CNRS UMR 6283, Institut des Molécules et Matériaux du Mans (IMMM), Avenue Olivier Messiaen, 72085, Le Mans Cedex 9, France

    Jérôme Lhoste & François Goutenoire

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  1. Firas Krichen
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Krichen, F., Walha, S., Lhoste, J. et al. Design of lanthanide metal organic frameworks incorporating dicarboxylate ligands. J Porous Mater 26, 1679–1689 (2019). https://doi.org/10.1007/s10934-019-00768-0

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