Mapping of Functional Groups in Metal-Organic Frameworks

Xueqian Kong, Hexiang Deng, Fangyong Yan, Jihan Kim, Joseph A. Swisher, Berend Smit, Omar M. Yaghi, Jeffrey A. Reimer, Mapping of Functional Groups in Metal-Organic Frameworks, Science 341 (6148), 882 (2013) 

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We determined the heterogeneous mesoscale spatial apportionment of functional groups in a series of multivariate metal-organic frameworks (MTV-MOF-5) containing BDC (1,4-benzenedicarboxylate) linkers with different functional groups, B (BDC-NH2), E (BDC-NO2), F (BDC-(CH3)2), H (BDC-(OC3H5)2), and I (BDC-(OC7H7)2), using solid-state nuclear magnetic resonance measurements combined with molecular simulations. Our analysis reveals that these methods discern between random (EF), alternating (EI, EHI), and various cluster (BF) forms of functional group apportionments. This combined synthetic, characterization, and computational approach predicts the adsorptive properties of crystalline MTV-MOF systems. This methodology, developed in the context of ordered frameworks, is a first step in resolving the more general problem of spatial disorder in other ordered materials, including mesoporous materials, functionalized polymers, and defect distributions within crystalline solids.

© Berend Smit 2013