2 H Solid-State NMR Spectroscopy Reveals the Dynamics of a Pyridine Probe Interacting with Coordinatively Unsaturated Metal Sites of MIL-100(Al) Metal-Organic Frameworks.

Coordinatively unsaturated metal sites (CUS) play an important role in catalysis by metal-organic frameworks (MOF). Being an intrinsic part of the framework the CUS take the role of acidic sites active in industrially relevant processes such as condensation or oxidation reactions. The key step of such reactions represents the coordination of the reagents to CUS. In MOFs the mechanism of the reagent interaction with CUS is poorly understood. Herein, we characterize the interaction of a widely used acidity probe pyridine with CUS of MIL-100(Al) MOF by means of the 2 H solid-state NMR spectroscopy. 2 H NMR reveals that pyridine species, which are interacting with CUS and the ones which are coordinated to the Al-OH site, exhibit different motional behavior. 2 H NMR line shape as well as T1 , T2 relaxation analyses for [D5 ]pyridine adsorbed in MIL-100(Al) allowed us to perform a detailed characterization of pyridine dynamics in both states including the kinetics of the exchange process between these adsorption states.