Functionalization of Zr-based MOFs with alkyl and perfluoroalkyl groups: the effect on the water sorption behavior.

Stability and sorption of Metal-Organic Frameworks (MOFs) towards water are critical in many applications, and can a priori be modulated through the introduction of suitable organic functional groups on their backbone. We report here the preparation of a series of Zr(iv)-based MOFs functionalized with alkyl and perfluoroalkyl groups and their characterization by X-ray powder diffraction, multi-nuclei ((1)H, (13)C, (19)F) solid state nuclear magnetic resonance analyses, and nitrogen sorption measurements at 77 K. Their water sorption behavior was evaluated at 298 K and related to their physico-chemical features, highlighting both the effect of the confinement and the nature of the functional groups on the hydrophilic/hydrophobic balance.