High and Tunable Proton Conduction in Six 3D-Substituted Imidazole Dicarboxylate-Based Lanthanide-Organic Frameworks

Six isostructural three-dimensional (3D) Ln(III)-organic frameworks, {[Ln₂(HMIDC)₂(μ₄-C₂O₄)(H₂O)₃]·4H₂O} [Ln^III = Gd^III (1), Eu^III (2), Sm^III (3), Nd^III (4), Pr^III (5), and Ce^III (6)], have been fabricated by using a multifunctional ligand of 2-methyl-1H-imidazole-4,5-dicarboxylic acid (H₃MIDC). Ln-metal-organic frameworks (MOFs) 1-6 present 3D structures and possess abundant H-bonded networks between imidazole-N atoms and coordinated and free water molecules. All the six Ln-MOFs demonstrate humidity- and temperature-dependent proton conductivity (σ) having the optimal values of 2.01 × 10^-3, 1.40 × 10^-3, 0.93 × 10^-3, 2.25 × 10^-4, 1.11 × 10^-4, and 0.96 × 10^-4 S·cm^-1 for 1-6, respectively, at 100 °C/98% relative humidity, in the order of Ce^III (6) < Pr^III (5) < Nd^III (4) < Sm^III (3) < Eu^III (2) < Gd^III (1). In particular, the σ for 1 is 1 order of magnitude higher than that for 6, and it enhances systematically according to the decreasing order of the ionic radius, indicating that the lanthanide-contraction tactics can effectively regulate the proton conductivity while retaining the proton conduction routes. This will offer valuable guidance for the acquisition of new proton-conducting materials. In addition, the outstanding water stability and electrochemical stability of such Ln-MOFs will afford a solid material basis for future applications.