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Characterization of Zn‐Containing Metal–Organic Frameworks by Solid‐State 67 Zn NMR Spectroscopy and Computational Modeling
Author(s) -
Sutrisno Andre,
Terskikh Victor V.,
Shi Qi,
Song Zhengwei,
Dong Jinxiang,
Ding San Yuan,
Wang Wei,
Provost Bianca R.,
Daff Thomas D.,
Woo Tom K.,
Huang Yining
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201201563
Subject(s) - nuclear magnetic resonance spectroscopy , spectroscopy , solid state nuclear magnetic resonance , zeolitic imidazolate framework , magic angle spinning , nmr spectra database , characterization (materials science) , zinc , nuclear magnetic resonance crystallography , metal organic framework , chemistry , molecule , imidazolate , molecular dynamics , materials science , crystallography , chemical physics , computational chemistry , nanotechnology , spectral line , fluorine 19 nmr , nuclear magnetic resonance , inorganic chemistry , organic chemistry , physics , quantum mechanics , adsorption , astronomy
Metal–organic 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 67 Zn solid‐state NMR (SSNMR) spectroscopy. This is because 67 Zn ( 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 67 Zn 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 67 Zn magic‐angle spinning (MAS) NMR spectra are highly sensitive to the local Zn environment and can differentiate non‐equivalent Zn sites. The 67 Zn NMR parameters can be predicted by theoretical calculations. Through the study of MOF‐5 desolvation, we show that with the aid of computational modeling, 67 Zn 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 67 Zn NMR spectroscopy is highly sensitive to the guest molecules present inside the cavities. Our work also shows that a combination of 67 Zn NMR data and molecular dynamics simulation can reveal detailed information on the distribution and the dynamics of the guest species. The present work establishes 67 Zn 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.