Energetic Systematics of Metal–Organic Frameworks: A Case Study of Al(III)-Trimesate MOF Isomers

Thermal stability and thermodynamic properties of aluminum(III)-1,3,5-benzenetricarboxylate (Al-BTC) metal–organic frameworks (MOFs), including MIL-96, MIL-100, and MIL-110, have been investigated through a suite of calorimetric and X-ray techniques. In situ high-temperature X-ray diffraction (HT-XRD) and thermogravimetric analysis coupled with differential scanning calorimetry (TGA-DSC) revealed that these MOFs undergo thermal amorphization prior to ligand combustion. Thermal stabilities of Al-BTC MOFs follow the increasing order MIL-110 < MIL-96 < MIL-100, based on estimated amorphization temperatures. Their thermodynamic stabilities were directly measured by high-temperature drop combustion calorimetry. Normalized (per mole of Al) enthalpies of formation (ΔH*f) of MIL-96, MIL-100, and MIL-110 from Al2O3, H3BTC, and H2O (only Al2O3 and H3BTC for MIL-100) were determined to be −56.9 ± 13.7, −36.2 ± 17.9, and 62.8 ± 11.6 kJ/mol·Al, respectively. Our results demonstrate that MIL-96 and MIL-100 are thermodynamically favorable, while MIL-110 is metastable, in agreement with thermal and hydrothermal stability trends. The enthalpic preferences of MIL-96 and MIL-100 may be attributed to their shared trinuclear μ3-oxo-bridged (Al3(μ3-O)) secondary building units (SBUs) promoting stabilization of Al polyhedra by the ligands within these frameworks, in comparison to the sterically strained Al8 octamer cluster cores formed in MIL-110. Furthermore, similar ΔH*f of MIL-96 and MIL-100 explain their concurrent formation as physical mixtures often encountered during synthesis, implying the importance of kinetic factors that may facilitate the formation of Al-BTC framework isomers. More importantly, the normalized formation enthalpies of Al-BTC MOF isomers follow a negative correlation with the ratio of charged coordinated substituents to linkers (normalized per mole of Al within the MOF formula unit), with enthalpic preference given to systems with smaller (O2– + OH–)/ligand ratios. This trend has been successfully extended to the previously measured ΔH*f of several Zn4O-based frameworks (e.g., MOF-5, MOF-5(DEF), MOF-177, UMCM-1), all of which have been found to be metastable with respect to their dense phases (ZnO, H2O, and ligands). The result suggests that carboxylate MOFs with higher metal coordination environments attain more enthalpic stabilization from the coordinated ligands. Thus, the formation of some lanthanide/actinide, transition metal, and main group carboxylate frameworks may be energetically more favored, which, however, requires further studies.