Understanding the multiscale self-assembly of metal-organic polyhedra towards functionally graded porous gels

Spatial heterogeneity and gradients within porous materials are key for controlling their mechanical properties and mass/energy transport, both in biological and synthetic materials. However, it is still challenging to induce such complexity in well-defined microporous materials such as crystalline metalorganic frameworks (MOFs). Here we show a method to generate a continuous gradient of porosity over multiple length scales by taking advantage of the amorphous nature of supramolecular polymers based on metal-organic polyhedra (MOPs). First, we use time-resolved dynamic light scattering (TRDLS) to elucidate the mechanism of hierarchical self-assembly of MOPs into colloidal gels and to understand the relationship between the MOP concentrations and the architecture of the resulting colloidal networks. These features directly impact the viscoelastic response of the gels and their mechanical strength. We then show that gradients of stiffness and porosity can be created within the gel by applying centrifugal force at the point of colloidal aggregation. These results with the creation of asymmetric and graded pore configuration in soft materials could lead to the emergence of advanced properties that are coupled to asymmetric molecule/ion transport as seen in biological systems.