Processing oriented metal–organic frameworks (MOFs) as thin films is a key challenge for their application to device fabrication. However, typical fabrication methods cannot generate precisely oriented crystals on commercially relevant scales (i.e., cm2). This limits access to applications that require anisotropic functional properties (e.g., separation, optics, and electronics). Currently, highly oriented copper‐based MOFs are synthesized via the addition of the organic MOF component to an ethanolic solution of manually aligned Cu(OH)2 nanobelt films. In this work, the optimization of a semi‐automatic method for the fabrication of precisely oriented MOF films that affords a 100% yield of high quality ceramic films at the centimeter scale is reported. This improved fabrication protocol will facilitate the progress of heteroepitaxially grown MOFs for molecular separators and micro‐opto‐electronic devices.

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...

Three molybdenum(VI) dioxido complexes [MoO 2 (L) 2 ] bearing Schiff base ligands were reacted with B(C 6 F 5 ) 3 to afford the corresponding adducts [MoO{OB(C 6 F 5 ) 3 }(L) 2 ], which were fully characterized. They exhibit Frustrated Lewis‐Pairs reactivity when reacting with silanes. Especially, the [MoO{OB(C 6 F 5 ) 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.

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