Seed-mediated evolution of hierarchical metal–organic framework quaternary superstructures

The idea of hierarchy, widely observed in natural and artificial worlds, has been extensively explored in chemistry and materials science. Similar to proteins which contain primary, secondary, tertiary and quaternary structures, varying levels of hierarchy in metal–organic framework (MOF) superstructures can also be achieved. In this work, we initiate a systematic study on the morphological evolution of hierarchical superstructures with the assistance of seeded growth and explore the assembly of multiple modular MOFs into superstructures with enhanced hierarchy and diversity. By utilizing MOF-74-III spherulite superstructures as seeds, multiple quaternary architectures were obtained depending on the lengths of organic linker precursors. The resulting superstructures with superior hierarchy represent a unique porous material which contains multiple modules with diverse morphologies. To the best of our knowledge, this is the first report that utilizes tertiary superstructures as seeds in MOF synthesis, which leads to unusual and diverse behaviors during secondary growth. This synthetic approach not only provides a facile method to establish hierarchy in porous materials, but also enables the fabrication of multiscale heterostructures through secondary growth on MOF seeds.