We present a toolbox for the rapid characterisation of powdered samples of paramagnetic metal-organic frameworks at natural abundance by 1 H-detected solid-state NMR. Very fast MAS rates at room and cryogenic temperatures and a set of tailored radiofrequency irradiation schemes help overcome the sensitivity and resolution limits often associated with the characterisation of MOF materials. We demonstrate the approach on DUT-8(Ni), a framework containing Ni2+ paddle-wheel units which can exist in two markedly different architectures. Resolved 1 H and 13 C resonances of organic linkers are detected and assigned in few hours with only 1-2 mg of sample at natural isotopic abundance, and used to rapidly extract information on structure and local internal dynamics of the assemblies, as well as to elucidate the metal electronic properties over an extended temperature range. The experiments disclose new possibilities for describing local and global structural changes and correlating them to electronic and magnetic properties of the assemblies.

Centre de Résonance Magnétique Nucléaire à Très Hauts Champs UMR 5082 CNRS ENS Lyon UCBL) Université de Lyon 69100 Villeurbanne France

Chair of Inorganic Chemistry 1 Technische Universität Dresden 01069 Dresden Germany

IFP Energies Nouvelles 69360 Solaize France

Institute of Inorganic Chemistry University of Regensburg 93040 Regensburg Germany

IRCELYON Université de Lyon 69100 Villeurbanne France

NMR Laboratory Faculty of Science Charles University Hlavova 8 12842 Prague Czech Republic

Present address 3P Instruments GmbH and Co KG Rudolf Diesel Strasse 12 85235 Odelzhausen Germany

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The role of surface deformation on responsivity of the pillared layer metal-organic framework DUT-8(Ni)