Introducing a Cantellation Strategy for the Design of Mesoporous Zeolite-like Metal–Organic Frameworks: Zr-sod-ZMOFs as a Case Study

Herein we report novel mesoporous zirconium-based metal–organic frameworks (MOFs) with zeolitic sodalite (sod) topology. Zr-sod-ZMOF-1 and -2 are constructed based on a novel cantellation design strategy. Distinctly, organic linkers are judiciously designed in order to promote the deployment of the 12-coordinated Zr hexanuclear molecular building block (MBB) as a tetrahedral secondary building unit, a prerequisite for zeolite-like nets. The resultant Zr-sod-ZMOFs exhibit mesopores with a diameter up to ≈43 Å, while the pore volume of 1.98 cm3·g–1 measured for Zr-sod-ZMOF-1 is the highest reported experimental value for zeolite-like MOFs based on MBBs as tetrahedral nodes.