Issue 1, 2024

Endogenous metal-ion dynamic nuclear polarization for NMR signal enhancement in metal organic frameworks

Abstract

Rational design of metal–organic framework (MOF)-based materials for catalysis, gas capture and storage, requires deep understanding of the host–guest interactions between the MOF and the adsorbed molecules. Solid-State NMR spectroscopy is an established tool for obtaining such structural information, however its low sensitivity limits its application. This limitation can be overcome with dynamic nuclear polarization (DNP) which is based on polarization transfer from unpaired electrons to the nuclei of interest and, as a result, enhancement of the NMR signal. Typically, DNP is achieved by impregnating or wetting the MOF material with a solution of nitroxide biradicals, which prevents or interferes with the study of host–guest interactions. Here we demonstrate how Gd(III) ions doped into the MOF structure, LaBTB (BTB = 4,4′,4′′-benzene-1,3,5-triyl-trisbenzoate), can be employed as an efficient polarization agent, yielding up to 30-fold 13C signal enhancement for the MOF linkers, while leaving the pores empty for potential guests. Furthermore, we demonstrate that ethylene glycol, loaded into the MOF as a guest, can also be polarized using our approach. We identify specific challenges in DNP studies of MOFs, associated with residual oxygen trapped within the MOF pores and the dynamics of the framework and its guests, even at cryogenic temperatures. To address these, we describe optimal conditions for carrying out and maximizing the enhancement achieved in DNP-NMR experiments. The approach presented here can be expanded to other porous materials which are currently the state-of-the-art in energy and sustainability research.

Graphical abstract: Endogenous metal-ion dynamic nuclear polarization for NMR signal enhancement in metal organic frameworks

Supplementary files

Article information

Article type
Edge Article
Submitted
06 Jul 2023
Accepted
23 Nov 2023
First published
02 Des 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2024,15, 336-348

Endogenous metal-ion dynamic nuclear polarization for NMR signal enhancement in metal organic frameworks

I. B. Moroz, Y. Feldman, R. Carmieli, X. Liu and M. Leskes, Chem. Sci., 2024, 15, 336 DOI: 10.1039/D3SC03456A

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