Metal‐Organic Frameworks: Coordination Polymer Nanoparticles and Macrostructures

Abstract

Organization at the atomic scale of metal cations by connecting them with organic linkers leads to the construction of hybrid crystalline microporous frameworks, also known as porous coordination polymers (PCPs). Owing to their high loading capacity and their chemical composition versatility, PCPs are attractive for applications such as gas storage, catalysis, sensing, proton conduction, or adsorptive separation. Beside the conventional research that aims at designing PCP crystal characteristics at the molecular scale, recent research efforts focused on the modulation of the crystal size and shape and on the synthesis of polycrystalline macrostructures with well‐defined morphologies. Indeed, a major challenge today is to develop strategies that allow the integration of PCPs into readily applicable devices, which fully exploit the attributes of these promising materials. The highly reactive surfaces of PCPs (composed of partially coordinated organic ligands or uncoordinated metal centers), the possible modulation of the coordination equilibrium at the crystal surface, and the large number of PCP frameworks available (implying a large range of possible synthesis conditions) make their synthesis compatible with a wide range of physicochemical and mechanical microfabrication methods. Syntheses of uniform PCP nanocrystal suspensions, crystal assemblies in the form of membranes, pattern surfaces, hollow spheres, coatings, or multiporous architectures were therefore reported. This chapter aims to review the most promising strategies reported so far to synthesize PCP nanocrystals and PCP‐based macrostructures and composites.