Synthesis, crystal structures and, magnetic and photoluminescence properties of lanthanide-based metal-organic frameworks constructed with 2,5-dihydroxybenzene-1,4-dicarboxylic acid

Abstract

Four new lanthanide(iii) coordination polymers (1-4) have been synthesized by using 2,5-dihydroxybenzene-1,4-dicarboxylate (Dhbdc, C8H6O62-) as a ligand and characterized by elemental analysis, infrared spectroscopy, TGA-DSC (Thermogravimetric Analysis-Differential Scanning Calorimetry) and single crystal X-ray diffraction studies. The isolated complexes include; [Ce(Dhbdc)(H2O)3Cl]n (1) and [Ln(Dhbdc)1.5(H2O)2]n·3n(C2H6O)·nH2O [Ln = Eu (2), Gd (3) and Tb (4)]. The structural analysis reveals that compound 1 is a two-dimensional polymer in which the cerium atoms are coordinated by six oxygen and two bridging chloride ions adopting a dodecahedral geometry. The compounds 2-4 are isomorphous and their extended structures consist of three-dimensional supramolecular frameworks encapsulating [001] channels occupied by the guest water and ethanol molecules. The metal atoms in 2-4 exhibit a square antiprism geometry. All these compounds have O-H⋯O hydrogen bonds originating from the coordinated water and solvent molecules that help to consolidate the structures. The compounds 1, 3 and 4 were investigated for magnetic properties and they exhibited weak antiferromagnetic coupling interactions between the lanthanides as per the Curie Weiss law. Anisotropic nature of 3 and 4 has been depicted as per magnetization versus field plots. Complex 4 behaves as a soft magnetic material as compared to 3. The luminescence studies indicate that compounds 2, 3 and 4 show ligand-centred fluorescence, which is significantly enhanced in the case of 4.