Crystal chemistry of aluminium carboxylates: From molecular species towards porous infinite three-dimensional networks

This account describes the crystal chemistry of aluminium in association with O-donor organic ligands, such as polycarboxylates. In this overview, molecular assemblies of aluminium-based species are discussed from the background knowledge of the polycationic species occurring in aqueous solution. The use of hydro/solvothermal synthetic route has led to the generation of novel crystalline extended three-dimensional networks, of metal-organic frameworks (MOFs) type, with consequent porosity properties. The first illustration of such materials was the aluminium-containing MIL-53 (Materials Institute Lavoisier – number 53), obtained from the hydrothermal reaction of aluminium salt source with terephthalic acid. This finding gave rise to the development of new series of porous aluminium MOF-like materials, some of which are now produced at the industrial scale. This review presents a description of various crystalline structures, from a classification based on the nuclearity of the aluminium-centered building units, involved in the construction of the framework.