Aliphatic-Bridged Early Lanthanide Metal–Organic Frameworks: Topological Polymorphism and Excitation-Dependent Luminescence

Abstract

Six new three-dimensional metal–organic frameworks based on early lanthanide(III) cations and trans-1,4-cyclohexanedicarboxylic acid (H2chdc) were obtained. Their crystal structures were determined by single-crystal X-ray diffraction analysis. The structure of [La2(H2O)4(chdc)3]·2DMF·H2O (1; DMF = N,N-dimethylformamide) contains one-dimensional infinite La(III)-carboxylate chains interconnected by cyclohexane moieties to form a highly porous polymeric lattice with 30% solvent accessible volume. Compounds [Ln2(phen)2(chdc)3]·0.75DMF (2Ln; Ln3+ = Ce3+, Pr3+, Nd3+ and Sm3+; phen = 1,10-phenanthroline) are based on binuclear carboxylate building blocks, which are decorated by chelate phenanthroline ligands and interconnected by cyclohexane moieties to form more dense isostructural coordination frameworks with primitive cubic pcu topology. Compound [Nd2(phen)2(chdc)3]·2DMF·0.67H2O (3) is based on secondary building units similar to 2Ln and contains a coordination lattice isomeric to 2Ln with a rare hexagonal helical snz topology. Thermal stability and luminescent properties were investigated. For 2Sm, a strong and nonmonotonous dependence of the luminescence color on the variation of excitation wavelength was revealed, changing its emission from pinkish red at λex = 340 nm to white at λex = 400 nm, and then to yellow at lower excitation energies. Such nonlinear behavior was rationalized in terms of the contribution of several different luminescence mechanisms. Thus, 2Sm is a rather rare example of a highly tunable monometallic lanthanide-based luminophore with possible applications in light-emitting devices and optical data processing.