A Series of Lanthanide-Based Metal–Organic
Frameworks Derived from Furan-2,5-dicarboxylate and Glutarate: Structure-Corroborated
Density Functional Theory Study, Magnetocaloric Effect, Slow Relaxation
of Magnetization, and Luminescent Properties
posted on 2019-05-30, 18:35authored byManesh Kumar, Lin-Hui Wu, Mukaddus Kariem, Antonio Franconetti, Haq Nawaz Sheikh, Sui-Jun Liu, Subash Chandra Sahoo, Antonio Frontera
Herein, through a
dual-ligand strategy, we report eight isorecticular lanthanide(III)
furan-2,5-dicarboxylic acid metal–organic frameworks (Ln-MOFs)
with the general formula {[Ln(2,5-FDA)0.5(Glu)(H2O)2]·xH2O}n [Ln = Sm (1), Eu (2),
Gd (3), Tb (4), Dy (5), Ho
(6), Er (7), and Yb (8); 2,5-FDA2– = furan-2,5-dicarboxylate and Glu2– = glutarate; x = 0.5 for 1, 2, and 4 and x = 0 for 3 and 5–8], synthesized under
solvothermal conditions by using an N,N′-dimethylformamide/H2O mixed solvent system. Crystallographic
data reveal that all eight Ln-MOFs 1–8 crystallize in the orthorhombic Pnma space group.
All of the MOFs are isostructural as well as isomorphous with distorted
monocapped square-antiprismatic geometry around the Ln1 metal center.
In Ln-MOFs 1–8, the 2,5-FDA2– and Glu2– ligands exhibit μ2-κ4,η1:η1:η1:η1 and μ3-κ5,η2:η1:η1:η1 coordination modes, respectively. Topologically, assembled Ln-MOFs 1–8 consist of the 2D cem topological type. The designed Ln-MOFs 1–8 are further explored for structure-corroborated density
functional theory study. Meanwhile, room temperature photoluminescence
properties of Ln-MOFs 2 and 4 and magnetic
properties of Ln-MOFs 3 and 5 have been
explored in detail. A highly intense, ligand-sensitized, Ln3+ f–f photoluminescence emission is exhibited by Ln-MOFs 2 [Eu3+ (red emission)] and 4 [Tb3+ (green emission)]. Magnetic studies suggest weak antiferro-
and ferromagnetic interactions between adjacent GdIII ions
in Ln-MOF 3, thereby displaying a large magnetocaloric
effect. The magnetic data measured at T = 2 K and
ΔH = 30 kOe depict that the −ΔSm value per unit mass reaches 32.1 J kg–1 K–1, which is larger than most
of the GdIII-based complexes reported. The alternating-current
susceptibility measurements on Ln-MOF 5 revealed that
out-of-phase signals are frequency- and temperature-dependent under
both 0 and 2 kOe direct-current fields, thereby suggesting a typical
slow magnetic relaxation behavior with two relaxation processes. This
is further supported by the Cole–Cole plots at 2.4–6
K.