From molecules to materials: Structural landscape of zinc terephthalates grown from solution

Nucleation of crystals from solution is a universal phenomenon that significantly impacts the development of advanced functional materials. In this context, metal organic frameworks (MOFs) which encompass a plethora of metal and multidentate organic ligand architectures offer potential applications in areas such as gas storage, gas separation and catalysis. The experimental and theoretical procedures employed, however, lack insights into the chemistry of molecular aggregation which is key to formulate synthetic protocols towards obtaining solids with desired structural features. Monitoring crystallization on a real timescale, especially at supersaturation involving a relatively small number of molecules, calls for advanced imaging and spectroscopic techniques supported by logical theoretical models. In this perspective, we have examined the crystal structures of zinc terephthalates grown from solution reported in the Cambridge Structural Database with an objective to rationalize the aggregation of molecular species occurring in the solution transforming into a crystal with a defined stoichiometry and dimensionality of zinc terephthalate coordination interaction. The structural chemistry described here addresses the influence of solvent, particularly water in the formation of MOF-5 and other related solids.

Automated summary

Crystallization from solution is a universal phenomenon that plays a significant role in the development of advanced functional materials. Metal organic frameworks (MOFs) have potential applications in gas storage, gas separation, and catalysis, but there are limitations in current experimental and theoretical procedures. Real-time monitoring of crystallization and understanding the chemistry of molecular aggregation are crucial for formulating synthetic protocols towards obtaining desired structural features in solids.