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

摘要

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 an{[Ln(2,5-FDA)(0.5)(Glu)-(H2O)(2)]center dot xH(2)O}(n) [Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy (5), Ho (6), Er (7), and Yb (8); 2,5-FDA(2-) = furan-2,5-dicarboxylate and Glu(2-)= 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 squareantiprismatic geometry around the Lnl metal center. In Ln-MOFs 1-8, the 2,5-FDA(2-) and Glu(2-) ligands exhibit mu(2)-kappa(4),eta(1):eta(1):eta(1):eta(1)and mu(3)-kappa(5),eta(2):eta(1):eta(1):eta(1): 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, Ln(3+) 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 Gd-III ions in Ln-MOF 3, thereby displaying a large magnetocaloric effect. The magnetic data measured at T = 2 K and Delta H = 30 kOe depict that the -Delta S-m value per unit mass reaches 32.1 J kg(-1) K-1, which is larger than most of the Ge-III-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 sugges