Continuous Variation of Lattice Dimensions and Pore Sizes in Metal-Organic Frameworks.

Continuous variation of lattice metric in metal-organic frameworks (MOFs) allows precise control over their chemical and physi-cal properties. It has been realized herein by a series of mixed-linker and Zr6-cluster-based MOFs, namely Continuously Variable MOFs (CVMOFs). Similar to the substitutional solid solutions, organic linkers with different lengths and various ratios were ho-mogeneously incorporated into a framework rather than forming separate phases or domains, which was manifested by single-crystal X-ray diffraction, powder X-ray diffraction, fluorescence quenching experiment and molecular simulations. The unit cell dimension, surface area and pore size of CVMOFs were precisely controlled by adopting different linker sets and linker ratios. We demonstrate that CVMOFs allow the continuous and fine tailoring of cell-edge lengths from 17.83 to 32.63 Å, Brunauer-Emmett-Teller (BET) surface areas from 585 to 3791 m2g-1, and pore sizes up to 15.9 Å. Furthermore, this synthetic strategy can be ap-plied to other MOF systems with various metal nodes, give rise to a variety of CVMOFs with unprecedented tunability.

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