4.8 Article

Docking in Metal-Organic Frameworks

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SCIENCE
卷 325, 期 5942, 页码 855-859

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AMER ASSOC ADVANCEMENT SCIENCE
DOI: 10.1126/science.1175441

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  1. U.S. Department of Defense [HDTRA1-08-10023]
  2. Northwestern University

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The use of metal-organic frameworks (MOFs) so far has largely relied on nonspecific binding interactions to host small molecular guests. We used long organic struts (similar to 2 nanometers) incorporating 34- and 36-membered macrocyclic polyethers as recognition modules in the construction of several crystalline primitive cubic frameworks that engage in specific binding in a way not observed in passive, open reticulated geometries. MOF-1001 is capable of docking paraquat dication (PQT(2+)) guests within the macrocycles in a stereoelectronically controlled fashion. This act of specific complexation yields quantitatively the corresponding MOF-1001 pseudorotaxanes, as confirmed by x-ray diffraction and by solid-and solution-state nuclear magnetic resonance spectroscopic studies performed on MOF-1001, its pseudorotaxanes, and their molecular strut precursors. A control experiment involving the attempted inclusion of PQT(2+) inside a framework (MOF-177) devoid of polyether struts showed negligible uptake of PQT(2+), indicating the importance of the macrocyclic polyether in PQT(2+) docking.

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