Dynamic network of intermolecular interactions in metal-organic frameworks functionalized by molecular machines

Molecular machines enable external control of structural and dynamic phenomena at the atomic level. To efficiently transfer their tunable properties into designated functionalities, a detailed understanding of the impact of molecular embedding is needed. In particular, a comprehensive insight is fundamental to design hierarchical multifunctional systems that are inspired by biological cells. Here, we applied an on-the-fly trained force field to perform atomistic simulations of a systematically modified rotaxane functionalized metal-organic framework. Our atomistic studies reveal a symmetric and asymmetric interplay of the mechanically bonded rings (MBRs) within the framework depending on the local environment. As a result, their translational motion is modulated ranging from fast oscillatory behavior to cooperative and potentially directed shuttling. The derived picture of competitive interactions, which influence the operation mechanism of the MBRs embedded in these soft porous materials, promotes the development of responsive functional materials, which is a key step toward intelligent matter.