Adsorption-desorption induced structural changes of Cu-MOF evidenced by solid state NMR and EPR spectroscopy

Adsorption-desorption induced structural changes of Cu(bpy)(H2O)2(BF4), (bpy) (bpy = 4,4 -bipyridine) [Cu-MOF] have been evidenced by combined NMR and EPR spectroscopy. Upon adsorption of probe molecules even at a few mbar, EPR spectra show that they are activated to form complexes at Cu(II) sites, which results in a change of the Cu-MOF's structure as indicated by a high-field shift of the 11B MAS NMR. After desorption, both EPR and 11B MAS NMR spectra evidenced that the structure of the Cu-MOF reversibly shifted to the original state. This observation indicates that MOFs can undergo structural changes during processes where adsorption-desorption steps are involved such as gas storage, separation, and catalysis.