Reticular Design of Precise Linker Installation into a Zirconium Metal-Organic Framework to Reinforce Hydrolytic Stability.
J Am Chem Soc
; 145(5): 3055-3063, 2023 Feb 08.
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| ID: mdl-36696577
ABSTRACT
Reticular chemistry allows for the rational assembly of metal-organic frameworks (MOFs) with designed structures and desirable functionalities for advanced applications. However, it remains challenging to construct multi-component MOFs with unprecedented complexity and control through insertion of secondary or ternary linkers. Herein, we demonstrate that a Zr-based MOF, NU-600 with a (4,6)-connected she topology, has been judiciously selected to employ a linker installation strategy to precisely insert two linear linkers with different lengths into two crystallographically distinct pockets in a one-pot, de novo reaction. We reveal that the hydrolytic stability of these linker-inserted MOFs can be remarkably reinforced by increasing the Zr6 node connectivity, while maintaining comparable water uptake capacity and pore-filling pressure as the pristine NU-600. Furthermore, introducing hydrophilic -OH groups into the linear linker backbones to construct multivariate MOFs can effectively shift the pore-filling step to lower partial pressures. This methodology demonstrates a powerful strategy to reinforce the structural stability of other MOF frameworks by increasing the connectivity of metal nodes, capable of encouraging developments in fundamental sciences and practical applications.
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J Am Chem Soc
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2023
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Article