High resolution solid state NMR in paramagnetic metal-organic frameworks

C A Klug; M W Swift; J B Miller; J L Lyons; A Albert; M Laskoski; C M Hangarter

doi:10.1016/j.ssnmr.2022.101811

High resolution solid state NMR in paramagnetic metal-organic frameworks

Solid State Nucl Magn Reson. 2022 Aug:120:101811. doi: 10.1016/j.ssnmr.2022.101811. Epub 2022 Jun 26.

Authors

C A Klug¹, M W Swift², J B Miller³, J L Lyons², A Albert³, M Laskoski³, C M Hangarter³

Affiliations

¹ Chemistry Division, U.S. Naval Research Laboratory, Washington, DC, USA. Electronic address: christopher.klug@nrl.navy.mil.
² Materials Science Division, U.S. Naval Research Laboratory, Washington, DC, USA.
³ Chemistry Division, U.S. Naval Research Laboratory, Washington, DC, USA.

PMID: 35792451
DOI: 10.1016/j.ssnmr.2022.101811

Abstract

We study the metal-organic framework (MOF) ZIF-67 with ¹H and ¹³C nuclear magnetic resonance (NMR). In addition to the usual orbital chemical shifts, we observe spinning sideband manifolds in the NMR spectrum due to hyperfine interactions of the paramagnetic cobalt with ¹H and ¹³C. Both orbital and paramagnetic chemical shifts are in good agreement with values calculated from first principles, allowing high-confidence assignment of the observed peaks to specific sites within the MOF. Our measured resonance shifts, line shapes, and spin lattice relaxation rates are also consistent with calculated values. We show that molecules in the pores of the MOF can exhibit high-resolution NMR spectra with fast spin lattice relaxation rates due to dipole-dipole couplings to the Co²⁺ nodes in the ZIF-67 lattice, showcasing NMR spectroscopy as a powerful tool for identification and characterization of "guests" that may be hosted by the MOF in electrochemical and catalytic applications.

Keywords: Contact shift; Dipole-dipole shift; MOF; NMR; Paramagnetic; ZIF-67.

Published by Elsevier Inc.