ABSTRACT
Fundamental knowledge on the intrinsic timescale of structural transformations in photo-switchable metal-organic framework films is crucial to tune their switching performance and to facilitate their applicability as stimuli-responsive materials. In this work, for the first time, an integrated approach to study and quantify the temporal evolution of structural transformations is demonstrated on an epitaxially oriented DMOF-1-on-MOF film system comprising azobenzene in the DMOF-1 pores (DMOF-1/AB). We employed time-resolved Grazing Incidence Wide-Angle X-Ray Scattering measurements to track the structural response of the DMOF-1/AB film upon altering the length of the azobenzene molecule by photo-isomerization (trans-to-cis, 343 nm; cis-to-trans, 450 nm). Within seconds, the DMOF-1/AB response occurred fully reversible and over several switching cycles by cooperative photo-switching of the oriented DMOF-1/AB crystallites as confirmed further by infrared measurements. Our work thereby suggests a new avenue to elucidate the timescales and photo-switching characteristics in structurally responsive MOF film systems.
ABSTRACT
Three molybdenum(VI) dioxido complexes [MoO2(L)2] bearing Schiff base ligands were reacted with B(C6F5)3 to afford the corresponding adducts [MoO{OB(C6F5)3}(L)2], which were fully characterized. They exhibit Frustrated Lewis-Pairs reactivity when reacting with silanes. Especially, the [MoO{OB(C6F5)3}(L)2] complex with L=2,4-dimethyl-6-((phenylimino)methyl)phenol proved to be active as catalyst for the hydroalkylation of aryl alkenes with organohalides and for the Atom-Transfer Radical Addition (ATRA) of organohalides to aliphatic alkenes. A series of gem-dichloride and gem-dibromide compounds with potential for further derivatization were synthesized from simple alkenes and organohalides, like chloroform or bromoform, using low catalyst loading.
