Docking in metal-organic frameworks

• Main Authors: Miljanić, Ognjen Š., Knobler, Carolyn B., Yaghi, Omar M., Li, Qiaowei, Zhang, Wenyu, Sue, Chi Hau, Zhao, Yanli, Liu, Lihua, Stoddart, J. Fraser
• Other Authors: School of Physical and Mathematical Sciences
• Format: Article
• Language: English
• Published: 2011
• Subjects: DRNTU::Science::Chemistry::Organic chemistry::Organometallic compounds
• Online Access: https://hdl.handle.net/10356/93946; http://hdl.handle.net/10220/6961
• Institution: Nanyang Technological University

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 (~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 (PQT2+) 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 PQT2+ inside a framework (MOF-177) devoid of polyether struts showed negligible uptake of PQT2+, indicating the importance of the macrocyclic polyether in PQT2+ docking.