A Series of Lanthanide−Organic Frameworks Based on 2-Propyl-1H-imidazole-4,5-dicarboxylate and Oxalate: Syntheses, Structures, Luminescence, and Magnetic Properties

Abstract

A family of self-assembly lanthanide−organic coordination polymers with both rigid and flexible ligands formulated as {[Ln2(Hpimda)2(μ4-C2O4)·2H2O]·4H2O} n (Ln = Sm (1), Eu (2), Tb (3), Dy (4), Ho (5), Er (6), H3pimda = 2-propyl-1H-imidazole-4,5-dicarboxylic acid) has been synthesized from the reactions of H3pimda with trivalent lanthanide salts in the presence of oxalate as coligand. X-ray diffraction analysis reveals that these complexes are isomorphous and isostructural, and each forms a novel three-dimensional (3D) frameworks structure, in which the metalloligands' two-dimensional (2D) networks were constructed from the lanthanide ion, 2-propyl-imidazole-dicarboxylate as well as oxalate ligands, and the oxalate further acts as a pillar to link the [Ln(Pimda)(oxo)] 2D grids to generate the 3D open frameworks, leaving one-dimensional channels, which are occupied by water clusters displaying an intricate array. The luminescence emission spectra of the complexes vary depending on which lanthanide ion is present. In addition, compounds 3, 4, and 5 exhibited weak but significant ferromagnetic couplings within the two adjacent magnetic centers bridged through oxalato, whereas dominant antiferromagnetic interaction was observed in the erbium compound of 6, respectively.

Lanthanide coordination compounds with 2,2′-bipyridine-6,6′-dicarboxylate: Synthesis, crystal structure, luminescence and magnetic property

“…4. The v M T values at 300 K are 16.70, 25.27, 29.51, 28.67 and 23.45 cm 3 K mol À1 for 1, 2, 3, 4 and 5, respectively, which are slightly larger than the expected values for two isolated Ln 3+ ions ( 8 S 7/2 , g = 2 for 1; 7 F 6 , g J = 3/2 for 2; 6 H 15/2 , g J = 4/3 for 3; 5 I 8 , g J = 5/4 for 4; 4 I 15/2 , g J = 6/5 for 5) [55,56]. Upon cooling the v M T values decrease gradually to the values of 15.01 cm 3 mol À1 K at 1.8 K for 1, which is a typical paramagnetic behavior.…”

Crystal structure of poly-[triaqua-(μ3-3,4,5,6-tetrafluoro-1,2-phthalato-κ4 O:O′:O′′,O′′′) (2,3,4,5-tetrafluoro-benzoato-κ2 O,O′) praseodymium(III)], C15H7F8O9Pr

“…This contributes to their potential application in areas of luminescent probe, catalysis, gas storage, nonlinear optics, magnetism [3,4]. Lanthanide coordination polymers based on polycarboxylic ligands are prevalent because of their high structural stability and various coordination modes [5,6].…”

Crystal structure of poly[(.3-4-(4-oxopyridin-1(4H)-yl)phtalato- κ4O,O':O'':O''')-(μ2-2-carboxy-5-(4-oxopyridin-1(4H)-yl)benzoato- κ3O,O':O'')samarium(III)], C26H15N2O10Sm

“…The design and construction of lanthanide-metal-organic frameworks (Ln-MOFs) based on the judicious selection of ligands and metal ions have become avery attractive field of research in coordination chemistrya nd crystale ngineering [1][2][3]. Nowadays, lanthanide coordination polymers based on polycarboxylic ligands are prevalent because of their high structural stability and various coordination modes [4,5].…”