Characterization of Zn-containing MOFs by Solid-state 67Zn NMR and Computational Modeling

Metal\u2013organic frameworks (MOFs) are an extremely important class of porous materials with many applications. The metal centers in many important MOFs are zinc cations. However, their Zn environments have not been characterized directly by 67Zn solid-state NMR (SSNMR) spectroscopy. This is because 67Zn (I=5/2) is unreceptive with many unfavorable NMR characteristics, leading to very low sensitivity. In this work, we report, for the first time, a 67Zn natural abundance SSNMR spectroscopic study of several representative zeolitic imidazolate frameworks (ZIFs) and MOFs at an ultrahigh magnetic field of 21.1 T. Our work demonstrates that 67Zn magicangle spinning (MAS) NMR spectra are highly sensitive to the local Zn environment and can differentiate nonequivalent Zn sites. The 67Zn NMR parameters can be predicted by theoretical calculations. Through the study of MOF-5 desolvation, we show that with the aid of computational modeling, 67Zn NMR spectroscopy can provide valuable structural information on the MOF systems with structures that are not well described. Using ZIF-8 as an example, we further demonstrate that 67Zn NMR spectroscopy is highly sensitive to the guest molecules present inside the cavities. Our work also shows that a combination of 67Zn NMR data and molecular dynamics simulation can reveal detailed information on the distribution and the dynamics of the guest species. The present work establishes 67Zn SSNMR spectroscopy as a new tool complementary to X-ray diffraction for solving outstanding structural problems and for determining the structures of many new MOFs yet to come.Peer reviewed: YesNRC publication: Ye