Ternary MOF-on-MOF heterostructures with controllable architectural and compositional complexity via multiple selective assembly

Assembly of different metal-organic framework (MOF) building blocks into hybrid MOF-on-MOF heterostructures is promising in chemistry and materials science, however the development of ternary MOF-on-MOF heterostructures with controllable architectural and compositional complexity is challenging. Here we report the synthesis of three types of ternary MOF-on-MOF heterostructures via a multiple selective assembly strategy. This strategy relies on the choice of one host MOF with more than one facet that can arrange the growth of a guest MOF, where the arrangement is site-selective without homogenous growth of guest MOF or homogenous coating of guest on host MOF. The growth of guest MOF on a selected site of host MOF in each step provides the opportunity to further vary the combinations of arrangements in multiple steps, leading to ternary MOF-on-MOF heterostructures with tunable complexity. The developed strategy paves the way towards the rational design of intricate and unprecedented MOF-based superstructures for various applications. Assembly of MOF-on-MOF hybrids with complex structures and properties is of interest, but achieving sophisticated ternary heterostructures is challenging. Here, the authors synthesize three types of ternary MOF-on-MOF heterostructures with tunable complexity via a multiple selective assembly strategy.