Higher Magnetic Fields, Finer MOF Structural Information: ¹⁷O Solid-State NMR at 35.2 T

The spectroscopic study of oxygen, a vital element in materials, physical, and life sciences, is of tremendous fundamental and practical importance. ¹⁷O solid-state NMR (SSNMR) spectroscopy has evolved into an ideal site-specific characterization tool, furnishing valuable information on the local geometric and bonding environments about chemically distinct and, in some favorable cases, crystallographically inequivalent oxygen sites. However, ¹⁷O is a challenging nucleus to study via SSNMR, as it suffers from low sensitivity and resolution, owing to the quadrupolar interaction and low ¹⁷O natural abundance. Herein, we report a significant advance in ¹⁷O SSNMR spectroscopy. ¹⁷O isotopic enrichment and the use of an ultrahigh 35.2 T magnetic field have unlocked the identification of many inequivalent carboxylate oxygen sites in the as-made and activated phases of the metal-organic framework (MOF) α-Mg₃(HCOO)₆. The subtle ¹⁷O spectral differences between the as-made and activated phases yield detailed information about host-guest interactions, including insight into nonconventional O···H-C hydrogen bonding. Such weak interactions often play key roles in the applications of MOFs, such as gas adsorption and biomedicine, and are usually difficult to study via other characterization routes. The power of performing ¹⁷O SSNMR experiments at an ultrahigh magnetic field of 35.2 T for MOF characterization is further demonstrated by examining activation of the MIL-53(Al) MOF. The sensitivity and resolution enhanced at 35.2 T allows partially and fully activated MIL-53(Al) to be unambiguously distinguished and also permits several oxygen environments in the partially activated phase to be tentatively identified. This demonstration of the very high resolution of ¹⁷O SSNMR recorded at the highest magnetic field accessible to chemists to date illustrates how a broad variety of scientists can now study oxygen-containing materials and obtain previously inaccessible fine structural information.