Metal-Organic Framework Thin Films as Ideal Matrices for Azide Photolysis in Vacuum

Studies on reactions in solutions are often hampered by solvent effects. In addition, detailed investigation on kinetics is limited to the small temperature regime where the solvent is liquid. Here, we report the in situ spectroscopic observation of UV-induced photochemical reactions of aryl azides within a crystalline matrix in vacuum. The matrices are formed by attaching the reactive moieties to ditopic linkers, which are then assembled to yield metal-organic frameworks (MOFs) and surface-mounted MOFs (SURMOFs). These porous, crystalline frameworks are then used as model systems to study azide-related chemical processes under ultrahigh vacuum (UHV) conditions, where solvent effects can be safely excluded and in a large temperature regime. Infrared reflection absorption spectroscopy (IRRAS) allowed us to monitor the photoreaction of azide in SURMOFs precisely. The in situ IRRAS data, in conjunction with XRD, MS, and XPS, reveal that illumination with UV light first leads to forming a nitrene intermediate. In the second step, an intramolecular rearrangement occurs, yielding an indoloindole derivative. These findings unveil a novel pathway for precisely studying azide-related chemical transformations. Reference experiments carried out for solvent-loaded SURMOFs reveal a huge diversity of other reaction schemes, thus highlighting the need for model systems studied under UHV conditions.