Structure Tuning of Hafnium Metal–Organic Frameworks through a Mixed Solvent Approach

The recent development of water-stable metal–organic frameworks (MOFs) has significantly broadened the application scope of this emerging type of porous material. Structure tuning of hafnium MOFs is less studied compared with zirconium MOFs. In this work, we report the synthesis of a mesoporous hafnium MOF, csq-MOF-1, through finely tuning the solvent mixture ratio. The successful synthesis of csq-MOF-1 also relies on the linker flexibility as linker bending and a symmetry decrease were observed in this framework as compared to its structural isomer NPF-300 (Hf). The mesoporous feature and permanent porosity were determined by the N2 adsorption at 77 K. Such a hierarchical pore feature is expected to enable a variety of applications through encapsulation of large functional molecules. The synthetic strategy of utilizing a mixed solvent and flexible linker is expected to inspire the development of new hafnium MOFs with diverse topological structures.