Nanoporous Films with Oriented Arrays of Molecular Motors for Photoswitching the Guest Adsorption and Diffusion

Molecular motors are fascinating nanomachines. However, constructing smart materials from such functional molecules presents a severe challenge in material science. Here, we present a bottom‐up layer‐by‐layer assembly of oriented overcrowded‐alkene molecular motors forming a crystalline metal–organic framework thin film. While all stator parts of the overcrowded‐alkene motors are oriented perpendicular to the substrate, the rotors point into the pores, which are large enough allowing for the light‐induced molecular rotation. Taking advantage of the thin film's transparency, the motor rotation and its activation energy are determined by UV/Vis spectroscopy. As shown by gravimetric uptake experiments, molecular motors in crystalline porous materials are used, for the first time, to control the adsorption and diffusion properties of guest molecules in the pores, here, by switching with light between the (meta‐)stable states. The work demonstrates the potential of designed materials with molecular motors and indicates a path for the future development of smart materials.