Integration of a Molecular Rotor and a Photoswitch in a Metal−Organic Framework

High Resolution Image Download MS PowerPoint Slide Porous dynamic crystalline materials are highly valued for the connection between internal dynamics and functional performance, yet the controlled integration and interaction between multiple dynamic components within a single framework remain a fundamental challenge. Here, we employed the zirconium-based metal−organic framework UiO-68, constructed from a terphenyl dicarboxylate linker ( L rot ), as a base scaffold to integrate a second dynamic component: a pyrrolo[3,2-b]pyrrole-derived linker with two azobenzene moieties ( L azo ) into a family of L rot: L azo multivariate metal-organic frameworks (MTV-MOFs). After irradiation, solid-state UV-Vis and deuterium solid-state NMR revealed that both components exhibit independent dynamics within the framework. This work incorporates rotors and photoswitches into an MTV-MOF, and subsequent studies show that the uptake of hexafluorobenzene enables a L azo photoisomeric-dependent effect on the rotational behavior of L rot . The results allow us to expand the scope of responsive multidynamic crystalline materials toward the design of artificial molecular factories.