Three-Dimensional Lanthanide−Organic Frameworks Based on Di-, Tetra-, and Hexameric Clusters

Three-dimensional lanthanide−organic frameworks formulated as (CH3)2NH2[Ln(pydc)2]·1/2H2O [Ln3+ = Eu3+ (1a) or Er3+ (1b); pydc2− corresponds to the diprotonated residue of 2,5-pyridinedicarboxylic acid (H2pydc)], [Er4(OH)4(pydc)4(H2O)3]·H2O (2), and [PrIII2PrIV1.25O(OH)3(pydc)3] (3) have been isolated from typical solvothermal (1a and 1b in N,N-dimethylformamide - DMF) and hydrothermal (2 and 3) syntheses. Materials were characterized in the solid state using single-crystal X-ray diffraction, thermogravimetric analysis, vibrational spectroscopy (FT-IR and FT-Raman), electron microscopy, and CHN elemental analysis. While synthesis in DMF promotes the formation of centrosymmetric dimeric units, which act as building blocks in the construction of anionic ∞3{[Ln(pydc)2]−} frameworks having the channels filled by the charge-balancing (CH3)2NH2+ cations generated in situ by the solvolysis of DMF, the use of water as the solvent medium promotes clustering of the lanthanide centers: structures of 2 and 3 contain instead tetrameric [Er4(μ3-OH)4]8+ and hexameric |Pr6(μ3-O)2(μ3-OH)6| clusters which act as the building blocks of the networks, and are bridged by the H2−xpydcx− residues. It is demonstrated that this modular approach is reflected in the topological nature of the materials inducing 4-, 8-, and 14-connected uninodal networks (the nodes being the centers of gravity of the clusters) with topologies identical to those of diamond (family 1), and framework types bct (for 2) and bcu-x (for 3), respectively. The thermogravimetric studies of compound 3 further reveal a significant weight increase between ambient temperature and 450 °C with this being correlated with the uptake of oxygen from the surrounding environment by the praseodymium oxide inorganic core.