Investigation of the preparation and reactivity of metal–organic frameworks of cerium and pyridine-2,4,6-tricarboxylate

Abstract

The synthesis of three coordination polymers of cerium(III) and the ligand pyridine-2,4,6-tricarboxylate (PTC) is reported. Two of the materials crystallise under hydrothermal conditions at 180 °C, with [Ce(PTC)(H₂O)₂]·1.5H₂O, (1), being formed on extended periods of reaction time, 3 days or longer, and Ce(PTC)(H₂O)₃, (2), crystallising after 1 day. Both phases contain Ce(III) but are prepared using the Ce(IV) salt Ce(SO₄)₂·4H₂O as reagent. Under solvothermal conditions (mixed water-N,N-dimethylformamide (DMF)), the phase [Ce(PTC)(H₂O)(DMF)]·H₂O (3) is crystallised. The structures of the three materials are resolved by single crystal X-ray diffraction, with the phase purity of the samples determined by powder X-ray diffraction and thermogravimetric analysis. (1) is constructed from helical chains cross-linked by the PTC linkers to give a three-dimensional structure that contains clusters of water molecules in channels that are hydrogen-bonded to each other and to additional waters that are coordinated to cerium. (2) also contains nine-coordinate cerium but these are linked to give a dense framework, in which water is directly coordinated to cerium. (3) contains corner-shared nine-coordinate cerium centres, linked to give a framework in which Ce-coordinated DMF fills space. Upon heating the material (1) in air all water is irreversibly lost to give a poorly crystalline anhydrous phase Ce(PTC), as deduced from X-ray thermodiffractometry and thermogravimetric analysis. The material (1), however, is hydrothermally stable, and is also stable under oxidising conditions, where immersion in 30% H₂O₂ gives no loss in crystallinity. Oxidation of around 50% of surface Ce to the +4 oxidation state is thus possible, as evidenced by X-ray photoelectron spectroscopy, which is accompanied by a colour change from yellow to orange. Photocatalytic activity of (1) is screened and the material shows effective degradation of methyl orange.