The Influence of Chemical Modification on Linker Rotational Dynamics in Metal–Organic Frameworks

The robust synthetic flexibility of metal–organic frameworks (MOFs) offers a promising class of tailorable materials, for which the ability to tune specific physicochemical properties is highly desired. This is achievable only through a thorough description of the consequences for chemical manipulations both in structure and dynamics. Magic angle spinning solid‐state NMR spectroscopy offers many modalities in this pursuit, particularly for dynamic studies. Herein, we employ a separated‐local‐field NMR approach to show how specific intraframework chemical modifications to MOF UiO‐66 heavily modulate the dynamic evolution of the organic ring moiety over several orders of magnitude. Ringrotationen in MOFs wurden in Festkörper‐NMR‐Experimenten unter Probenrotation um den magischen Winkel durch dipolare Dephasierung über die Rotorperiode detektiert. Informationen zur Dynamik in Metall‐organischen Gerüsten sind wichtig, weil die Geschwindigkeit der Rotationsbewegung des Linkers die Sorptions‐ und Trenneigenschaften von MOFs beeinflusst.