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.

A chiral self-sorting photoresponsive coordination cage based on overcrowded alkenes.

In recent years, increasing efforts have been devoted to designing new functional stimuli-responsive supramolecular assemblies. Here, we present three isomeric supramolecular coordination complexes consisting of a Pd2L4 stoichiometry. As shown by NMR, CD and X-ray studies, as well as DFT calculations, these complexes form cage-like structures by chiral self-sorting. Photochromic ligands derived from first generation molecular motors enable light-driven interconversion between the three isomers. Two of the isomers were able to form host-guest complexes opening up new prospects toward stimuli-controlled substrate binding and release.

Photo-Powered Collapse of Supramolecular Polymers Based on an Overcrowded Alkene Switch.

A supramolecular polymer was constructed from a light-driven overcrowded alkene switch modified with two alkylated gallic acid amide pendants (MSP-1). Upon UV irradiation, stable MSP-1 isomerized into unstable MSP-2, which induced the effective collapse of well-defined cross-linked supramolecular polymers, and the reassembly can be realized by aging at low temperature.