Series of Highly Stable Lanthanide-Organic Frameworks Constructed by a Bifunctional Linker: Synthesis, Crystal Structures, and Magnetic and Luminescence Properties.

Abstract

By utilizing a preselected functional ligand produced by 1 H-imidazole-4,5-dicarboxylic acid, three isostructural lanthanide coordination polymers (CPs), denoted as {[Ln2(OH)2(L)2]·(DMF)·(H2O)4} n (Ln = Gd (1), Eu (2), Dy (3); L = 1-(4-carboxybenzyl)imidazole-4-carboxylic acid), containing a 1D infinite [Ln4(OH)4] subchain have been successfully constructed. The highly connected mode between the multifunctional ligand and 1D building units is responsible for the exceptional chemical stability of three lanthanide CPs. In addition, a study of the magnetic properties reveals that 1 displays a large magnetic entropy change (-Δ Sm = 30.33 J kg-1 K-1 with T = 2 K and Δ H = 7 T). Furthermore, genetic algorithm and quantum Monte Carlo methods were combined to simulate the magnetic coupling parameters of compound 1, shedding light on the effect of linking bridges on magnetic propagation. 2 shows intense luminescence in the range of 350-710 nm. Comparably, magnetic studies of 3 reveal the existence of a metamagnetic transformation from an antiferromagnetic interaction to a ferromagnetic interaction along with a decrease in temperature. Through fitting of the results of HF-EPR measurements, a component of the g tensor is obtained, g|| = 16.4(5), indicating the large anisotropy of 3.