Introducing a photo-switchable azo-functionality inside Cr-MIL-101-NH2 by covalent post-synthetic modification

For the first time an azo functionality was covalently introduced into a MOF by post-synthetic modification. The reaction of Cr-MIL-101-NH2 with p-phenylazobenzoylchloride (1) and 4-(phenylazo)-phenylisocyanate (2) as the reactants led to the compounds Cr-MIL-101_amide and Cr-MIL-101_urea, with the azo groups protruding into the mesoporous cages. XRPD and N-2 sorption measurements confirm the intactness of the framework and the successful covalent modification was proven by IR- and NMR-spectroscopy. Furthermore, cis/trans isomerisation upon irradiation with light was demonstrated by UV/Vis spectroscopy. More distinct changes in the UV/Vis spectra were observed for Cr-MIL-101_amide compared to Cr-MIL-101_urea, while the degree of functionalization, i.e. the number of reacted NH2-groups, seems to have a less pronounced effect. The variation of the sorption properties due to the cis/trans isomerisation was proven by methane adsorption measurements.