Synthesis, Crystal Structures And, Magnetic and Photoluminescence Properties of Lanthanide-based Metal-organic Frameworks Constructed with 2,5-dihydroxybenzene-1,4-dicarboxylic Acid
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Four new lanthanide(iii) coordination polymers (1-4) have been synthesized by using 2,5-dihydroxybenzene-1,4-dicarboxylate (Dhbdc, CHO ) 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)(HO)Cl] (1) and [Ln(Dhbdc)(HO)] ·3(CHO)·HO [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 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.
A new mode of luminescence in lanthanide oxalates metal-organic frameworks.
Alzard R, Siddig L, Saleh N, Nguyen H, Nguyen Q, Ho T Sci Rep. 2022; 12(1):18812.
PMID: 36335280 PMC: 9637143. DOI: 10.1038/s41598-022-23658-z.